WO2018182127A1 - Photosensitive resin composition, and color filter and image display device prepared by using same - Google Patents

Abstract

A photosensitive resin composition according to the present invention comprises: an alkali soluble resin; and scattering particles having an average particle diameter of 30-500nm and comprising metal oxide. The alkali soluble resin comprises one or more selected from a group consisting of a first cardo-based binder resin which comprises a compound represented by chemical formula (1) and is polymerized and a second cardo-based binder resin which comprises a compound represented by chemical formula (2) and is polymerized. The photosensitive resin composition according to the present invention can provide excellent color reproduction properties and high luminous efficiency and can produce a high-quality image.

Description

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

The present invention relates to a photosensitive resin composition comprising specific scattering particles and an alkali-soluble resin, a color filter and an image display device manufactured using the same.

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 particular, as color filters are used in various fields, including various image display devices, not only excellent pattern characteristics but also high color reproducibility and excellent performance such as high brightness and high contrast ratio are required. A color filter manufacturing method using a self-luminous photosensitive resin composition is proposed.

Republic of Korea Patent Publication No. 2013-0000506 relates to a display device, a plurality of wavelength conversion particles for converting the wavelength of light; And a color converter including a plurality of color filter particles that absorb light having a predetermined wavelength in the light.

However, in the case of a color filter including a quantum dot, the efficiency of the color filter may be somewhat degraded as the efficiency of the quantum dot, in particular, the blue quantum dot is reduced, and in the case of the blue quantum dot, there is a problem that the overall manufacturing cost increases. .

Therefore, development of the photosensitive resin composition which can prevent the fall of the efficiency of a blue pixel, and can lower manufacturing cost is calculated | required.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Republic of Korea Patent Publication No. 2013-0000506 (2013.01.03.)

An object of this invention is to provide the photosensitive resin composition which can prevent the fall of the efficiency of a blue pixel, and can lower manufacturing cost.

In addition, the present invention is to provide a color filter and an image display device including a blue pixel layer manufactured using the photosensitive resin composition described above. Specifically, the present invention is to provide a color filter and an image display device excellent in image quality, viewing angle, durability, reliability.

The photosensitive resin composition according to the present invention for achieving the above object is an alkali-soluble resin; And scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm; wherein the alkali-soluble resin comprises a first cardo-based binder resin and a compound represented by the following Chemical Formula 2, including the compound represented by the following Chemical Formula 1. It characterized in that it comprises at least one selected from the group consisting of a second cardo-based binder resin to be polymerized.

[Formula 1]

[Formula 2]

In Formula 1,

R1 and R2 are each independently

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

R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In Formula 2,

R4 and R5 are each independently

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

R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms.

In addition, the present invention provides a color filter made of the photosensitive resin composition described above and an image display device including the same.

The photosensitive resin composition of this invention has the advantage that provision of the outstanding color reproduction characteristic and light efficiency is possible.

In addition, the color filter made of the photosensitive resin composition of the present invention and an image display device including the same can ensure high quality image quality, excellent viewing angle, high durability, and reliability, and can reduce manufacturing cost.

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

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

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

<Photosensitive resin composition>

One embodiment of the present invention, alkali-soluble resin; And scattering particles comprising a metal oxide having an average particle diameter of 30 to 500 nm; wherein the alkali-soluble resin comprises a first cardo-based binder resin and a compound represented by the following Chemical Formula 2, including the compound represented by the following Chemical Formula 1. It relates to a photosensitive resin composition comprising at least one selected from the group consisting of a second cardo-based binder resin to be polymerized, including.

[Formula 1]

[Formula 2]

In Formula 1,

R1 and R2 are each independently

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

R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In Formula 2,

R4 and R5 are each independently

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

R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms.

Alkali soluble resin

The photosensitive resin composition of the present invention is selected from the group consisting of a first cardo-based binder resin that is polymerized including a compound represented by the following Formula 1 and a second cardo-based binder resin that is polymerized including a compound represented by the following Formula 2 It includes one or more.

[Formula 1]

[Formula 2]

In Formula 1,

R1 and R2 are each independently

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

R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

In Formula 2,

R4 and R5 are each independently

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

R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms.

The alkali-soluble resin has reactivity and alkali solubility by the action of light or heat. Specifically, the alkali-soluble resin may act as a binder resin for scattering particles, and may be soluble in an alkaline developer used in a developing step for manufacturing a color filter.

The alkali-soluble resin according to the present invention includes the first cardo-based binder resin polymerized by including the compound represented by the following Chemical Formula 1, thereby improving adhesion to the substrate and excellent development adhesion, thereby realizing a fine pattern for high resolution. There is an advantage to that.

[Formula 1]

Wherein R1 and R2 are each independently

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, R 3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably X is a hydroxyl group, and R 3 is a hydrogen atom or a methyl group.

The compound represented by Chemical Formula 1 may be synthesized using Chemical Formula 5 below, and the first cardo-based binder resin having alkali solubility may be obtained by further reacting an acid anhydride or an acid 2 anhydride compound.

[Formula 5]

For example, the compound represented by Chemical Formula 5 is mixed with epichlorohydrin and t-butylammonium bromide, heated and reacted with a solvent, followed by dropwise addition of an aqueous alkali solution, precipitation and separation to synthesize an epoxy compound, and synthesis. The resulting epoxy compound by reacting it with t-butylammonium bromide, acrylic acid, phenolic compound and solvent, and an acid anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, anhydride. Group consisting of hexahydrophthalic acid, methyl endomethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride or acid anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, biphenyl Aromatic polyhydric acids such as phenyl ether tetracarboxylic acid dianhydride It can be prepared by reacting at least one member selected from the group consisting of acids anhydride, but are not limited to this.

In addition, the alkali-soluble binder resin according to the present invention includes a second cardo-based binder resin polymerized by including the compound of the formula (2), thereby improving the adhesion to the substrate, excellent development adhesion and fine patterns for high resolution Enable to implement

[Formula 2]

In formula, R4 and R5 are each independently,

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group, R6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably X is a hydroxyl group, and R6 is a hydrogen atom or a methyl group.

The compound represented by Chemical Formula 2 may be synthesized using the following Chemical Formula 6, and the second cardo-based binder resin having alkali solubility may be obtained by further reacting an acid anhydride or an acid 2 anhydride compound.

[Formula 6]

For example, the compound represented by Chemical Formula 6 is mixed with epichlorohydrin, t-butylammonium bromide and a solvent, and then reacted by heating together, an aqueous alkali solution is added dropwise, precipitated and separated to synthesize an epoxy compound, and then synthesized. The resulting epoxy compound by reacting it with t-butylammonium bromide, acrylic acid, phenolic compound and solvent, and an acid anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, anhydride. Group consisting of hexahydrophthalic acid, methyl endomethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, or an acid dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polyhydric acids such as phenyl ether tetracarboxylic acid dianhydride It can be prepared by reacting at least one member selected from the group consisting of acids anhydride, but are not limited to this.

The position of the hydroxyl group (-OH) in the above formulas (5) and (6) is not particularly limited, and for example, may be 2-position, 3-position, and 4-position, and preferably 4-position (positioning is xanthene). And determine the carbon bonded to 1-top).

As a result, according to the position of the hydroxyl group (-OH) of the formula (5) or 6, the substitution position of R1 and R2 of the formula (1) or the substitution position of R4 and R5 of the formula (2) can be determined.

More specific examples of the compound represented by Formula 1 include 9,9-bis (3-cinnamic diester) fluorene, 9,9-bis ( 3-cinnamoyl, 4-hydroxyphenyl) fluorene (9,9-bis (3-cinnamoyl, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9, 9-bis (glycidyl methacrylate ether) fluorene, 9,9-bis (3,4-dihydroxyphenyl) fluorene disinnamic ester, 3,4-dihydroxyphenyl) fluorene dicinnamic ester , 6-diglycidyl methacrylate ether spiro (fluorene-9,9-xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xanthene)), 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), 9,9-bis (3,4-methacrylic diester) fluorene (9,9-bis (3,4-methacrylic diester) fluorene) It may be at least one selected, but is not limited thereto.

More specific examples of the compound represented by Formula 2 include 9,9-bis (3,4-methacrylic diester) xanthene, but are not limited thereto.

The acid value of the alkali-soluble binder resin may be 20 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g. In the case of having an acid value within 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. .

In the present invention, "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and can 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. 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.

It is preferable that it is 1.0-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said alkali-soluble resin, it is more preferable that it is 1.5-6.0. When the said molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] satisfy | fills the said range, since developability is excellent, it is preferable.

In one embodiment of the present invention, the cardo-based binder resin is included in 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the total photosensitive resin composition. Can be.

When the cardo-based binder resin is included in the above range, 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 it is difficult to reduce the film portion of the pixel portion of the exposed portion during development. It is preferable because there is an advantage that the omission property tends to be good.

In another embodiment of the present invention, the alkali-soluble resin may further include a cardo-based binder resin comprising at least one repeating unit of the following formula (3) and (4).

[Formula 3]

[Formula 4]

In Chemical Formulas 3 and 4,

P is each independently

R7 and R8 are each independently hydrogen, hydroxy group, thiol group, amino group, nitro group or halogen atom,

Ar1 is each independently a C6 to C15 aryl group,

Y is an acid anhydride residue,

Z is an acid 2 anhydride residue,

A is O, S, N, Si or Se,

a and b are each independently an integer of 1 to 6,

m and n are each independently an integer of 0 to 30,

Provided that m and n are not zero at the same time.

The halogen atom F, Cl, Br or I.

The aryl group may be a C6 to C15 monocyclic aryl group, or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, biphenyl group, terphenyl group, stilbenyl group and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

Y in Formula 3 is a residue of an acid anhydride, and an acid anhydride capable of introducing residue Y is not particularly limited. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, or hexahydride Hydrophthalic acid, methylene anhydride, methylenetetrahydrophthalic acid, chlororenic acid anhydride, methyltetrahydrophthalic anhydride, and the like can be given.

Z in the formula (4) is a residue of the acid 2 anhydride, acid 2 anhydride compound that can introduce the residue Z is not particularly limited, for example, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxylic acid Dianhydride, bitenyl ether tetracarboxylic acid dianhydride, cyclohexyl dianhydride, cyclobutyl acid dianhydride, and the like.

When the cardo-based binder resin according to the present invention is included in the photosensitive resin composition, there is an advantage that the light emission intensity, the diffusion rate and the external light reflectance may have more excellent effects.

When the alkali-soluble resin further comprises a cardo-based binder resin including at least one repeating unit selected from the group consisting of Formula 3 and Formula 4, the cardo-based binder resin is 100 parts by weight of the total alkali-soluble resin. 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 5 to 30 parts by weight.

When the cardo-based binder resin, which may be further included, is included in the above range, the light emission intensity, the diffusion rate, and the external light reflectance may be more excellent.

The cardo-based binder resin including at least one repeating unit of Formulas 3 and 4 may be prepared by, for example, the following method.

Synthesized by reacting any one of the compounds represented by Formula 7 to Formula 11 with an epoxy compound such as epichlorohydrin under a base catalyst or an acid catalyst and then reacted with a compound such as thiophenol, 1-thionaphthalene, 2-thionaphthalene By doing so, the compounds of the following Chemical Formulas 12 to 16 can be obtained.

Thereafter, a cardo-based binder resin including at least one repeating unit of Formulas 3 and 4 may be obtained by polymerizing a compound represented by Formulas 12 to 16 with carboxylic dianhydride.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Formulas 7 to 11, A, R7, and R8 are as defined in Formulas 3 and 4.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

In Chemical Formulas 12 to 16 c is an integer of 1 to 6,

A, Ar1, R7 and R8 are as defined in the formulas (3) and (4).

Specific examples of the above carboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3', 4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzo Phenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3- Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxylphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydrides, 9,9-bis (3,4-dicarboxyphenyl) fluorene acid dianhydrides, 9,9-bis {4- (3,4-dicar Ciphenoxy) phenyl} fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9, Tetracarboxylic dianhydride of aromatic rings, such as 10-perylene tetracarboxylic dianhydride and 2, 2-bis (3, 4- dicarboxy phenyl) hexafluoro propane dianhydride, and 1,2,3,4 Alicyclic tetracarboxes such as -cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride Acid dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride and the like.

The polymerization reaction may be performed at 100 to 130 ° C., or 110 to 120 ° C. for 2 hours to 24 hours, or 4 hours to 12 hours.

The carboxylic dianhydride may be added in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the monomer represented by Formula 12 to 16, for example.

The method for preparing a cardo-based binder resin including at least one repeating unit of Chemical Formulas 3 and 4 may include, for example, reacting by adding an end-capping agent after initiation of the polymerization reaction. have.

The end capping reaction may be performed at 100 to 130 ° C., or 110 to 120 ° C. for 30 minutes to 4 hours, or 1 hour to 3 hours, for example.

The end capping agent may be added in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the monomer represented by Formula 12 to 16, for example.

The end capping agent is preferably aromatic carboxylic anhydride, for example, phthalic anhydride, and the like, and in this case, excellent heat resistance, high permeability, and high refractive properties.

The weight average molecular weight of the cardo-based binder resin including at least one repeating unit of Formula 3 and Formula 4 is, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, more preferably 3,000 to It may be 10,000 g / mol, it is excellent in heat resistance within this range and the development speed of the photosensitive material and the development by the developing solution is suitable, there is an effect that the pattern formation is good.

The weight average molecular weight can be measured by gel permeation chromatography (GPC) method.

The degree of dispersion of the cardo-based binder resin resin including at least one repeating unit of Formulas 3 and 4 may be in the range of 1.0 to 5.0, preferably 1.5 to 4.0, and has excellent heat resistance within this range. And the development speed of the photosensitive material and the development by the developer is suitable, there is an effect that the pattern formation is good.

The dispersion degree of this description can be measured by GPC measuring method.

In another embodiment of the present invention, the alkali-soluble resin may further include an acrylic binder resin. When the alkali-soluble resin further includes the acrylic binder resin, it is preferable because the size of the minimum pattern that can be formed without loss of the pattern is small, which has advantages of high-resolution pattern implementation and pattern straightness.

Examples of the acrylic binder resin include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with the monomer.

As a carboxyl group-containing monomer, unsaturated carboxylic acids, such as unsaturated monocarboxylic acid, unsaturated polyhydric carboxylic acid, such as unsaturated polycarboxylic acid which has 1 or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, are mentioned, for example. Can be. 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. .

The acrylic binder resin may be included, for example, in an amount of 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble resin in total, in this case Fairness, such as implementation and pattern straightness, is advantageous.

The content of the alkali-soluble resin is usually in the range of 1 to 50 parts by weight, preferably 3 to 40 parts by weight, and still more preferably 5 to 30 parts by weight based on 100 parts by weight of the total photosensitive resin composition. When the content of the alkali-soluble resin satisfies the above range, 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 portion of the pixel portion of the exposed portion is less likely to occur during development. Since the omission of a part tends to be good, it is preferable.

Scattering particles

The photosensitive resin composition according to the present invention includes scattering particles containing a metal oxide having an average particle diameter of 30 to 500 nm.

In another embodiment of the present invention, 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, It may include one or more oxides selected from the group consisting of Ti, Sb, Sn, Zr, Nb, Ce, Ta, In and combinations thereof.

In another embodiment of the present invention, the metal oxide is 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 It may include one or more selected from the group consisting of -Al, Nb ₂ O ₃ , SnO, MgO and combinations thereof, and a material surface-treated with a compound having an unsaturated bond such as acrylate may be used if necessary. .

The scattering particles limit the content in the average particle diameter and the total composition to maximize the light emission intensity of the color filter.

In the present invention, the "average particle diameter" may be a number average particle diameter, and can be obtained from an image observed by, for example, a field emission runner electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, several samples can be extracted from the observed images of FE-SEM or TEM, and the diameters of these samples can be measured to obtain arithmetic mean values.

The metal oxide has an average particle diameter of 30 to 500 nm, preferably 30 to 300 nm. When the average particle diameter of the metal oxide satisfies the above range, the scattering effect is increased, and even though the photosensitive resin composition including the scattering particles does not include blue quantum dots, the blue oxide may serve as a blue pixel. Since the phenomenon which sinks in a composition can be prevented and the surface of a blue pattern layer of uniform quality can be obtained, it can adjust and use it suitably within the said range.

In another embodiment of the present invention, the scattering particles may be included in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 0.5 to 100 parts by weight of the total photosensitive resin composition. To 20 parts by weight. When the scattering particles are included in the above range, there is an advantage in that a color filter having excellent emission intensity can be manufactured. Specifically, when the scattering particles are included in the above range, it may be easy to ensure the emission intensity to be obtained, there is an advantage that can suppress the degradation of the composition stability.

Blue colorant

The photosensitive resin composition of this invention may further contain a blue coloring agent. Since the photosensitive resin composition according to the present invention further includes a blue colorant, the light of the light source reflected by the scattering particles, which will be described later, may be prevented from being reflected back by external light such as sunlight, thereby realizing high quality images. There is this.

The blue colorant may specifically include a blue pigment, and the blue pigment may specifically include a compound classified as a pigment in the color index (published by The society of Dyers and Colourists). Although the pigment of the same color index (CI) number is mentioned, It is not necessarily limited to these.

In another embodiment of the present invention, the blue colorant is C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, 60, 64, 76 and at least one blue pigment selected from the group consisting of a combination thereof; may include.

Among these, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, Pigment Blue 15: 6, C.I. It is preferable to include at least one member selected from the group consisting of Pigment Blue 16 in view of the effect of suppressing external light reflection and high color reproducibility.

In another embodiment of the present invention, the blue colorant may further include one or more selected from the group consisting of dyes and purple pigments.

The purple pigment is not limited thereto, for example, C.I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, and combinations thereof, and at least one selected from the group consisting of C.I. It is preferable to use pigment violet 23 in view of realizing high color reproducibility even through a small colorant content.

The dye may include a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists) or a known blue or purple dye described in a dye note (color dyed yarn).

For example, C.I. As solvent dyes,

C.I. Solvent blue 5, 35, 36, 37, 44, 45, 59, 67 and 70; And

C.I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49; and the like.

Among them, C.I. Solvent blue 35, 36, 44, 45 and 70; And C.I. It is preferred to include at least one member selected from the group consisting of solvent violet 13.

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; And

C.I. acid violet 6B, 7, 9, 17, 19, 66, etc. are mentioned.

Among them, C.I. Acid blue 80 and 90; And C.I. It is preferred to include at least one member selected from the group consisting of acid violet 66.

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; And

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

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

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 and 84;

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

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

In another embodiment of the present invention, the blue colorant may be included in 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the total photosensitive resin composition. have.

When the content of the blue colorant is less than the above range, it may be difficult to secure the external light reflection suppression effect to be obtained, on the contrary, when the content exceeds the above range, the increase in luminescence intensity may be slightly lowered, and the problem of lowering the viscosity stability of the composition may occur. Since it arises, it uses suitably within the said range.

In another embodiment of the present invention, the photosensitive resin composition is a photopolymerizable compound; Photopolymerization initiator; solvent; And it may further include one or more selected from the group consisting of additives.

Photopolymerizable compound

The photopolymerizable compound contained in the 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-vinyl py. A ralidone etc. are mentioned.

As a specific example of the said bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate and the like. Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound is used in the range of 1 to 30 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the total photosensitive resin composition. When the photopolymerizable compound satisfies the above range, the intensity and smoothness of the pixel portion tend to be good, which is preferable.

Photopolymerization initiator

It is preferable that the said photoinitiator used by this invention contains an acetophenone type compound.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2- methyl-1- phenyl propane- 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 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1 Oligomer of -one, etc. are mentioned, Preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 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 said active radical generating agent, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, etc. are mentioned, for example. As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether, etc. are mentioned, for example. As said 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-trimethyl benzophenone, etc. are mentioned. As said 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 said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -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 etc. are mentioned. 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.

Content of the said photoinitiator used for the photosensitive resin composition which concerns on this invention is 0.1-40 weight part normally with respect to the total amount of the said alkali-soluble resin and the said photopolymerizable compound based on 100 weight part of solid content whole, Preferably it is 1-30. Parts by weight. When it exists in the said range, since the said 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. The said photoinitiator adjuvant may be used in combination with the said photoinitiator, and is a compound used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by the said photoinitiator. An amine compound, an alkoxy anthracene type compound, a thioxanthone type compound etc. are mentioned as said photoinitiator starting adjuvant.

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 aids, 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 the said 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 photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of the 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, 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, methoxy butyl acetate and methoxy pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone , Ketones such as methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Esters such as methyl, and cyclic esters such as γ-butyrolactone. 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. The said solvent can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent in the photosensitive resin composition of this invention is 60-90 weight part normally with respect to 100 weight part of whole said photosensitive resin composition containing it, Preferably it is 70-85 weight part. When the content of the solvent satisfies the above range, the applicability tends to be good 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, or the like. It is preferable because there is.

additive

The photosensitive resin composition of this invention is a filler, another high molecular compound, a pigment dispersant as needed. It is also possible to use additives, such as an adhesion promoter, an antioxidant, a ultraviolet absorber, and an aggregation inhibitor.

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 additive may be used by those skilled in the art in addition to an appropriate amount within the scope that does not impair the effects of the present invention.

The method of preparing the photosensitive resin composition is not limited thereto, and for example, the photosensitive resin composition may be prepared 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 30 to 500 nm. At this time, a dispersing agent can be further used as needed, and some or all of alkali-soluble resin may be mix | blended. The remainder of alkali-soluble resin, a photopolymerizable compound, a photoinitiator, the other components used as needed, and the additional solvent as needed are further added to the obtained dispersion liquid (henceforth a mill base) so that it may become a predetermined concentration. To obtain the desired photosensitive resin composition.

<Color filter and image display device>

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

In the present invention, the photosensitive resin composition may be a photosensitive resin composition for forming a blue pattern layer. In this invention, the said photosensitive resin composition does not contain a quantum dot.

Since the color filter according to the present invention is made of the photosensitive resin composition described above instead of blue quantum dots, the manufacturing cost can be lowered, and there is an advantage of having an excellent viewing angle.

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 photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer is commonly known in the art. It can form by performing a method.

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 other words, the color filter according to the present invention may include the above-described blue pattern layer, and may further include a self-luminous pixel further comprising at least one selected from the group consisting of a red pattern layer and a green pattern layer.

The red pattern layer or the green pattern layer may include quantum dots and 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.

The scattering particles may include a metal oxide having an average particle diameter of 30 to 500 nm, and the content of the scattering particles and the metal oxide may be applied to the content of the scattering particles and the metal oxide included in the photosensitive resin composition according to the present invention. Can be.

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.

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 photosensitive resin composition described above, 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 a color filter including a blue pattern layer and the light source according to the present invention, there is an advantage of having excellent light emission intensity or viewing angle. 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 Alkali Soluble Resin

Synthesis Example  1: alkali soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) 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, followed by stirring, thereby raising the temperature of the flask to 90 ° C. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 h while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Then, a gas introduction tube was introduced to prevent bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas. 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.

Synthesis Example  2: Synthesis of Compound of Formula 1

In a 3000 ml three-neck round flask, 364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6 ''-dihydroxyspiro (fluorene-9,9-xantene) of formula 3 and t 0.4159 g of -butylammonium bromide was mixed, 2359 g of epichlorohydrin was added and heated to 90 ° C. The reaction was performed by liquid chromatography to give 3,6-dihydroxyspiro (fluorene-9,9-xanthene). Once completely consumed, it was cooled to 30 ° C. and a 50% aqueous solution of NaOH (3 equivalents) was added slowly, after analysis by liquid chromatography, epichlorohydrin was completely consumed, extracted with dichloromethane and washed three times, and then the organic layer was magnesium sulfate. After drying with dichloromethane, 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 (1).

Synthesis Example  3: Synthesis of Compound of Formula 2

In a 3000 ml three-neck round flask, 364.4 g of 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9H-xanthene-9,9-diyl) diphenol) of formula 4 and t- 0.4159 g of butylammonium bromide was mixed, 2359 g of epichlorohydrin was added thereto, and the mixture was heated and reacted at 90 ° C. After liquid chromatography, 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenol) is completely depleted. Aqueous% aqueous NaOH 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 (2).

Synthesis Example  4 : Cardo system  Synthesis of 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 1 of Synthesis 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 binder resin. Loss of anhydride was confirmed by IR spectrum. Resin A-1 whose solid acid value was 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 4,530.

Synthesis Example  5: Cardo system  Synthesis of Binder Resin (A-2)

After dissolving by adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 2 of Synthesis Example 2, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed 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 binder resin. Loss of anhydride was confirmed by IR spectrum. Resin A-2 whose solid acid value was 98 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 3,830.

Synthesis Example  6: Cardo system  Synthesis of Binder Resin (B-1, B-2)

(1) Synthesis Example 6-1: 2,2 '-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis Synthesis of (oxirane) (2,2 '-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane))

Add 42.5 g of 9,9-bispehnolfluorene, add 220 ml of 2- (chloromethyl) oxirane and 100 mg of t-butylammonium bromide. The reaction mixture was stirred until the reaction mixture was exhausted at 0 ° C., and then distilled under reduced pressure, the temperature was lowered 30 ° C., dichloromethane was injected, and NaOH was slowly added thereto. The reaction was terminated by dropping 5% HCl, and the reaction was extracted and separated into layers, the organic layer was washed with water and washed to neutrality.The organic layer was dried over MgSO ₄ and concentrated under reduced pressure with a rotary evaporator. Dichloromethane was added to the concentrated product, methanol was added while stirring while raising the temperature to 40 ° C., and the solution temperature was lowered and stirred. After excessive, and vacuum-dried at room temperature to give a solid white powder 52.7g (94% yield).

(2) Synthesis Example 6-2: 3,3 '-((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis ((oxy)) bis (1-phenylthio) Propan-2-ol) (3,3 '-(((9H-Fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2- ol)) (BTCP) synthesis

The compound (1000g) of synthesis example 6-1, 524g of thiophenols, and 617g of ethanol were added and stirred. Triethylamine 328 g was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC) method, the reaction was terminated. After the reaction was completed, ethanol was removed by distillation under reduced pressure. The organics were dissolved in dichloromethane, washed with water, and then dichloromethane was removed by distillation under reduced pressure. The concentrated organics were dissolved in ethyl acetate and ether ether was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to give 945 g (64%) of pale yellow oil.

(3) Synthesis Example 6-3: Synthesis of Cardo-Based Binder Resin (B-1)

200 g of BTCP monomer dissolved in 50% PGMEA solvent was added thereto, and the temperature was increased to 115 ° C. 31.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-Biphenyltetracarboxylic dianhydride) was added dropwise at 115 ° C, and then maintained at 115 ° C for 6 hours. Stirred. 7.35 g of phthalic anhydride was added thereto, stirred for another 2 hours, and the reaction was terminated. After cooling, a binder resin having a weight average molecular weight of 3,500 g / mol was obtained.

 (4) Synthesis Example 6-4: Synthesis of Cardo-Based Binder Resin (B-2)

200 g of BTCP monomer dissolved in 50% PGMEA solvent was added thereto, and the temperature was increased to 115 ° C. After dropping 21.1 g of Pyromellitic dianhydride at 115 ° C., the mixture was stirred while maintaining 115 ° C. for 6 hours. 7.35 g of Phthalic anhydride was added thereto, followed by further stirring for 2 hours to terminate the reaction. After cooling, a binder solution having a weight average molecular weight of 4,500 g / mol was obtained.

At this time, the weight average molecular weight (Mw) measurement of resin was performed on condition of the following using GPC method.

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)

Example  1 to 46 Comparative example  1 to 10: Preparation of Photosensitive Resin Composition

According to the composition of Tables 1 to 4, a photosensitive resin composition according to Examples and Comparative Examples was prepared (Table 1 shows scattering particles, Table 2 shows blue and purple colorants, Tables 3 to 7 Examples Photosensitive resin composition according to the above, Tables 8 and 9 show the composition and content of the photosensitive resin composition according to the comparative example).

	Kinds	Average particle diameter	product name	manufacturer
E-1	TiO 2	220 nm	TR-88	Huntsmansa
E-2	TiO 2	30 nm	TTO-55 (C)	Ishihara
E-3	TiO 2	130 nm	PT-401L	Ishihara
E-4	TiO 2	210 nm	CR-63	Ishihara
E-5	TiO 2	500 nm	R-960	Dupont
E-6	TiO 2	900 nm	R-902	Dupont
E-7	Al 2 O 3	50 nm	0.05㎛ Aluminapowder	Allied
E-8	Al 2 O 3	300 nm	0.3㎛ Aluminapowder	Allied
E-9	Al 2 O 3	1000 nm	1.0㎛ Aluminapowder	Allied
E-10	SiO 2	2000 nm	SYLYSIA 220A	Fujisa

	Kinds	product name	manufacturer
B-1	C.I.Pigment B15: 6	Fastogen Blue EP-7S	DIC
B-2	C.I.Pigment B15: 4	Fastogen Blue 5424	DIC
B-3	C.I.Pigment B15: 3	Heliogen Blue L 7072 D	BASF
B-4	C.I.Pigment B16	Pigment Blue 16	CPMA
V-1	C.I.Pigment V23	Fastogen Super Violet 140V	DIC

		Example
		One	2	3	4	5	6	7	8	9	10
Scattering particles	E-1	0.50	5.00	10.00	15.00	20.00	10.00	10.00	10.00	10.00	-
	E-2	-	-	-	-	-	-	-	-	-	10.00
	E-3	-	-	-	-	-	-	-	-	-	-
	E-4	-	-	-	-	-	-	-	-	-	-
	E-5	-	-	-	-	-	-	-	-	-	-
	E-6	-	-	-	-	-	-	-	-	-	-
	E-7	-	-	-	-	-	-	-	-	-	-
	E-8	-	-	-	-	-	-	-	-	-	-
	E-9	-	-	-	-	-	-	-	-	-	-
	E-10	-	-	-	-	-	-	-	-	-	-
Alkali soluble resin	Cardo resin (A-1)	9.75	9.75	9.75	9.75	9.75	6.83	4.88	2.93	-	-
	Cardo-based resin (A-2)	-	-	-	-	-	-	-	-	9.75	4.88
	Acrylic resin (A)	-	-	-	-	-	2.93	4.88	6.83	-	4.88
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29
Solvent 3 )		80.96	76.46	71.46	66.46	61.46	71.45	71.45	71.45	71.46	71.45

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Example
		11	12	13	14	15	16	17	18	19	20	21
Scattering particles	E-1	-	-	-	-	-	-	-	-	-	0.10	50.00
	E-2	-	-	-	-	-	-	-	-	-	-	-
	E-3	10.00	-	-	-	-	-	-	-	-	-	-
	E-4	-	10.00	10.00	10.00	10.00	10.00	-	-	-	-	-
	E-5	-	-	-	-	-	-	10.00	-	-	-	-
	E-6	-	-	-	-	-	-	-	-	-	-	-
	E-7	-	-	-	-	-	-	-	10.00		-	-
	E-8	-	-	-	-	-	-	-	-	10.00	-	-
	E-9	-	-	-	-	-	-	-	-	-	-	-
	E-10	-	-	-	-	-	-	-	-	-	-	-
Alkali soluble resin	Cardo resin (A-1)	9.75	9.75	-	-	-	-	9.75	9.75	9.75	9.75	9.75
	Cardo-based resin (A-2)	-	-	9.75	8.78	4.88	0.98	-	-	-	-	-
	Acrylic resin (A)	-	-	-	0.98	4.88	8.78	-	-	-	-	-
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29
Solvent 3 )		71.46	71.46	71.46	71.45	71.45	71.45	71.46	71.46	71.46	81.36	31.46

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Example
		22	23	24	25	26	27	28	29	30	31
Scattering particles	E-1	0.50	5.00	10.00	15.00	20.00	10.00	10.00	10.00	10.00	10.00
	E-2	-	-	-	-	-	-	-	-	-	-
	E-3	-	-	-	-	-	-	-	-	-	-
	E-4	-	-	-	-	-	-	-	-	-	-
	E-5	-	-	-	-	-	-	-	-	-	-
	E-6	-	-	-	-	-	-	-	-	-	-
	E-7	-	-	-	-	-	-	-	-	-	-
	E-8	-	-	-	-	-	-	-	-	-	-
	E-9	-	-	-	-	-	-	-	-	-	-
	E-10	-	-	-	-	-	-	-	-	-	-
Blue colorant	B-1	0.50	3.00	3.00	3.00	3.00	5.00	15.00	30.00	-	-
	B-2	-	-	-	-	-	-	-	-	3.00	-
	B-3	-	-	-	-	-	-	-	-	-	3.00
	B-4	-	-	-	-	-	-	-	-	-	-
Purple colorant	V-1	-	-	-	-	-	-	-	-	-
Alkali soluble resin	Cardo resin (A-1)	9.75	9.75	9.75	9.75	9.75	6.83	4.88	2.93	-	-
	Cardo-based resin (A-2)	-	-	-	-	-	-	-	-	9.75	4.88
	Acrylic resin (A)	-	-	-	-	-	2.93	4.88	6.83	-	4.88
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29
Solvent 3 )		80.46	73.46	68.46	63.46	58.46	66.45	56.45	41.45	68.46	68.45

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Example
		32	33	34	35	36	37	38	39	40	41
Scattering particles	E-1	10.00	10.00	10.00	-	-	-	-	-	-	-
	E-2	-	-	-	10.00	-	-	-	-	-	-
	E-3	-	-	-	-	10.00	-	-	-	-	-
	E-4	-					10.00		-	-	10.00
	E-5	-	-	-	-	-	-	10.00		-	-
	E-6	-	-	-	-	-	-	-	-	-	-
	E-7	-	-	-	-	-	-	-	10.00	-	-
	E-8	-	-	-	-	-	-	-	-	10.00	-
	E-9	-	-	-	-	-	-	-	-	-	-
	E-10	-	-	-	-	-	-	-	-	-	-
Blue colorant	B-1	-	-	2.70	3.00	3.00	3.00	3.00	3.00	3.00	3.00
	B-2	-	-	-	-	-	-	-	-	-	-
	B-3	3.00	-	-	-	-	-	-	-	-	-
	B-4		3.00	-	-	-	-	-	-	-	-
Purple colorant	V-1	-	-	0.30	-	-	-	-	-	-	0.50
Alkali soluble resin	Cardo resin (A-1)	9.75	9.75	-	-	-	-	9.75	9.75	9.75	9.75
	Cardo-based resin (A-2)	-	-	9.75	8.78	4.88	0.98	-	-	-	-
	Acrylic resin (A)	-	-	-	0.98	4.88	8.78	-	-	-	-
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29	2.29
Solvent 3 )		68.46	68.46	68.46	68.45	68.45	68.45	68.46	68.46	68.46	67.96

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Example
		42	43	44	45	46
Scattering particles	E-1	10	10	10	10	10
	E-2	-	-	-	-	-
	E-3	-	-	-	-	-
	E-4	-	-	-	-	-
	E-5	-	-	-	-	-
	E-6	-	-	-	-	-
	E-7	-	-	-	-	-
	E-8	-	-	-	-	-
	E-9	-	-	-	-	-
	E-10	-	-	-	-	-
Blue colorant	B-1	3	3	3	3	3
	B-2	-	-	-	-	-
	B-3	-	-	-	-	-
	B-4	-	-	-	-	-
Purple colorant	V-1	-	-	-	-	-
Alkali soluble resin	Cardo resin (A-1)	4.88	4.88	-	-	3.25
	Cardo-based resin (A-2)	-	-	4.88	4.88	-
	Cardo Resin (B-1)	4.88	-	4.88	-	3.25
	Cardo Resin (B-2)	-	4.88	-	4.88	-
	Acrylic resin (A)	-	-	-	-	3.25
Photopolymerizable compound 1 )		6.5	6.5	6.5	6.5	6.5
Initiator 2 )		2.29	2.29	2.29	2.29	2.29
Solvent 3 )		68.45	68.45	68.45	68.45	68.46

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Comparative example
		One	2	3	4
Scattering particles	E-1	-	-	-	-
	E-2	-	-	-	-
	E-3	-	-	-	-
	E-4	-	-	-	-
	E-5	-	-	-	-
	E-6	15	10.00		-
	E-7	-	-	-	-
	E-8	-	-	-	-
	E-9	-	-	10.00
	E-10	-	-	-	10.00
Alkali soluble resin	Cardo resin (A-1)	-	-	-	-
	Cardo-based resin (A-2)	-	-	-	-
	Acrylic resin	9.75	9.75	9.75	9.75
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29
Solvent 3 )		66.46	71.46	71.46	71.46

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

		Comparative example
		5	6	7	8	9	10
Scattering particles	E-1	0.10	10.00	-	-	-	-
	E-2	-	-	-	-	-	-
	E-3	-	-	-	-	-	-
	E-4	-	-	-	-	-	-
	E-5	-	-	-	-	-	-
	E-6	-	-	10.00		-	-
	E-7	-	-	-	-	-	-
	E-8	-	-	-	-	-	-
	E-9	-	-	-	10.00	-	-
	E-10	-	-	-	-	10.00	10.00
Blue colorant	B-1	-	55.00	-	-	-	-
	B-2	-	-	55.00	-	-	-
	B-3	-	-	-	55.00	-	-
	B-4	-	-	-	-	55.00	-
Purple colorant	V-1	-	-	-	-	-	55.00
Alkali soluble resin	Cardo resin (A-1)	-	-	-	-	-	-
	Cardo-based resin (A-2)	-	-	-	-	-	-
	Acrylic resin (A)	9.75	9.75	9.75	9.75	9.75	9.75
Photopolymerizable compound 1 )		6.50	6.50	6.50	6.50	6.50	6.50
Initiator 2 )		2.29	2.29	2.29	2.29	2.29	2.29
Solvent 3 )		81.36	16.46	16.46	16.46	16.46	16.46

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

2) Initiator (D): Irgaqure-907 (manufactured by BASF Corporation)

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

Manufacture of color filter

The color filter was manufactured using the photosensitive resin composition manufactured according to the said Example and the comparative example. That is, each of the photosensitive resin composition 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 horizontal × vertical 20 mm × 20 mm squares and a line / space pattern of 1 to 100 μm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm ² under an atmospheric atmosphere using an ultrahigh 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.

Experimental Example  1: Development speed, sensitivity, pattern stability test of color filter

The development speed, sensitivity, and pattern stability of the color filter manufactured by the photosensitive resin composition according to the Examples and Comparative Examples were measured. Evaluation criteria for each experiment are as follows. The measurement results are shown in Table 10.

Development speed (sec): Time taken for the first non-exposure part to dissolve in the developer during development <Spray Developer HPMJ method>

Sensitivity: The degree of formation of a flawless thin film of the sensitivity mask fine pattern (1 to 60) (the lower the value, the better the sensitivity).

Pattern Stability: Pattern error after exposure of pattern mask at low exposure amount (20-100mJ)

○: no error on the pattern

Δ: pattern error of 1 to 2

×: 3 or more errors on the pattern

(○, △, × are the results confirmed by the optical microscope of the three-dimensional surface shape machine)

Experimental Example 2 Measurement Experiment of Solvent Resistance and Heat Resistance of Color Filter

Evaluation indicating whether the color filter made of the photosensitive resin composition according to the Examples and Comparative Examples through the heat resistance and solvent resistance measurement experiment, stable to the heat and solvent used in the manufacture of the color filter or when manufacturing the liquid crystal display device It was. The measurement results are shown in Table 10.

Solvent resistance evaluation: The color filter prepared above is immersed in solvent NMP (1-methyl- 2-pyrrolidinone) for 30 minutes, and the color change before and after evaluation is calculated and compared. The equation used at this time is calculated by the following equation (1) representing the color change in the three-dimensional colorimeter defined by L ^* , a ^* , b ^* .

Heat resistance evaluation: The color filter manufactured by the above method was calculated by Equation (1) to measure the color change before and after heating after heating for 2 hours in a heating oven at 230 ℃.

Equation ^{(1) △ Eab * = [} (△ L *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

○: less than ΔEab ^* = 1,

Δ: ΔEab ^* = 1 to 3,

×: ΔEab ^* = 3 or more

Experimental Example  3: micro pattern formation experiment

The size of the pattern, which was obtained through a line / space pattern mask designed to 100 μm among color filters manufactured using the photosensitive resins according to the above examples and comparative examples, was measured by OM equipment (ECLIPSE LV100POL Nikon). . The measurement results are shown in Table 10.

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.

	Developing speed	Sensitivity	Pattern stability	Fine pattern	Heat resistance	Solvent resistance
Example 1	31	10	○	14	△	○
Example 2	29	9	○	12	○	○
Example 3	28	9	○	11	○	○
Example 4	30	8	○	6	○	○
Example 5	30	12	○	2	△	○
Example 6	27	14	○	12	○	○
Example 7	23	12	○	10	○	○
Example 8	19	11	○	13	○	○
Example 9	25	9	○	8	○	○
Example 10	21	12	○	11	○	○
Example 11	28	11	○	9	○	○
Example 12	29	8	○	10	○	○
Example 13	25	12	○	8	○	○
Example 14	23	9	○	6	○	○
Example 15	21	13	○	10	○	○
Example 16	16	14	○	9	○	○
Example 17	28	9	○	8	○	○
Example 18	27	11	○	7	○	○
Example 19	30	10	○	6	○	○
Example 20	28	11	○	7	○	○
Example 21	27	13	○	10	○	○
Example 22	28	10	○	14	△	○
Example 23	26	9	○	12	○	○
Example 24	25	9	○	11	○	○
Example 25	27	8	○	6	○	○
Example 26	27	12	○	2	○	○
Example 27	24	14	○	12	○	○
Example 28	20	12	○	10	○	○
Example 29	16	11	○	13	○	○
Example 30	22	9	○	8	○	○
Example 31	18	12	○	11	○	○
Example 32	25	11	○	9	○	○
Example 33	26	8	○	10	○	○
Example 34	22	12	○	8	○	○
Example 35	20	9	○	6	○	○
Example 36	18	13	○	10	○	○
Example 37	13	14	○	9	○	○
Example 38	25	9	○	8	○	○
Example 39	24	11	○	7	○	○
Example 40	24	11	○	7	○	○
Example 41	27	10	○	6	○	○
Example 42	25	9	○	10	○	○
Example 43	26	9	○	9	○	○
Example 44	26	10	○	9	○	○
Example 45	24	11	○	10	○	○
Example 46	25	10	○	9	○	○
Comparative Example 1	9	60	×	-10	△	×
Comparative Example 2	10	55	△	-2	×	×
Comparative Example 3	8	50	×	-One	△	×
Comparative Example 4	11	60	×	-5	×	×
Comparative Example 5	25	15	△	23	×	○
Comparative Example 6	6	59	×	-10	△	×
Comparative Example 7	7	58	×	-20	×	△
Comparative Example 8	5	48	×	-15	△	×
Comparative Example 9	5	49	×	-13	△	×

In Table 10, it can be seen that the scattering particles of the metal oxides formed fine patterns well when the average particle diameter was in the range of 30 to 500 nm. In the comparative example, it was confirmed that the formation of the micropattern was difficult.

In addition, it was confirmed that the sensitivity, pattern stability, fine pattern, and reliability were very excellent when the cardo binder was introduced or when the cardo binder and the acrylic binder were used together when the acrylic binder resin alone was applied.

Experimental Example  4: emission intensity measurement

Light scattered through a 365 nm tube-type 4 W UV irradiator (VL-4LC, VILBER LOURMAT) on a portion formed in a 20 × 20 mm square pattern among color filters prepared using the scattering particles and the photosensitive resin according to the comparative example. The converted region was measured, and the Examples and Comparative Examples measured the emission intensity in the 450 nm region using a Spectrum meter (Ocean Optics). The measurement results are shown in Table 11.

Experimental Example  5: viewing angle measurement

The optical intensity according to the viewing angle under the transmissive conditions was formed on the portion formed in the pattern of 20 × 20 mm square among the color filters manufactured using the photosensitive resin compositions prepared according to the above Examples and Comparative Examples (GC-5000L, Nippon). Denshoku) was used, and the diffusion rate was calculated using the following equation (2). The measurement results are shown in Table 11.

Equation (2)

Diffusion rate = (I70 + I20) / 2 × I5 × 100

I means light intensity measured at the viewing angle.

Experimental Example  6: reflectance measurement

Spectrophotometer CM- was used to measure the light reflectance under light-transmitting conditions on the portion formed in the pattern of 20 × 20 mm square in the color filter manufactured using the photosensitive resin composition prepared according to Examples 22 to 46 and Comparative Examples 5 to 10. It was measured using 3600A (Konica Minolta Co., Ltd.) and the measurement results are shown in Table 8.

	Luminous intensity	Diffusion rate	External light reflectance
Example 1	28500	20.5	-
Example 2	34700	43.5	-
Example 3	31800	78.3	-
Example 4	29800	78.1	-
Example 5	28200	84.3	-
Example 6	31300	53.5	-
Example 7	26500	78.9	-
Example 8	23900	48.6	-
Example 9	36500	48.6	-
Example 10	28500	82.1	-
Example 11	34800	33.6	-
Example 12	30800	78.1	-
Example 13	27800	82.1	-
Example 14	34200	51.3	-
Example 15	31300	72.6	-
Example 16	26500	74.9	-
Example 17	21900	43.5	-
Example 18	36500	49.7	-
Example 19	25900	80.7	-
Example 20	38600	42.1	-
Example 21	271960	44.8	-
Example 22	28500	20.5	3.1
Example 23	34700	43.5	3.8
Example 24	31800	78.3	2.8
Example 25	29800	78.1	2.6
Example 26	28200	84.3	2.7
Example 27	31300	53.5	3.6
Example 28	26500	78.9	3.8
Example 29	23900	48.6	3.1
Example 30	36500	48.6	2.1
Example 31	28500	82.1	2.5
Example 32	34800	33.6	2.9
Example 33	30800	78.1	3.1
Example 34	27800	82.1	3.8
Example 35	34200	51.3	3.6
Example 36	31300	72.6	3.2
Example 37	26500	74.9	2.9
Example 38	21900	43.5	2.1
Example 39	36500	49.7	1.9
Example 40	25900	80.7	2.3
Example 41	25900	80.7	3.8
Example 42	36988	82	2.5
Example 43	37586	82.3	2.6
Example 44	38124	83.1	2.8
Example 45	37201	82.9	2.7
Example 46	36907	82.6	2.7
Comparative Example 1	17700	18.7	-
Comparative Example 2	28200	8.5	-
Comparative Example 3	19200	4.5	-
Comparative Example 4	16400	8	-
Comparative Example 5	41200	2.1	8.2
Comparative Example 6	8850	18.7	0.8
Comparative Example 7	8850	8.5	1.2
Comparative Example 8	9600	4.5	1.6
Comparative Example 9	8200	7.8	0.9
Comparative Example 10	8200	8.2	1.8

The higher the measured light emission intensity, the higher the light efficiency. In Table 11, it can be seen that the scattering particles of the metal oxides had an average particle diameter in the range of 30 to 500 nm, and the emission intensity was improved compared to the comparative example.

The higher the measured diffusion, the better the viewing angle. In Table 11, the scattering particles of the metal oxide was found that the viewing angle is improved compared to the comparative example in the case of using the scattering particles of the metal oxide 30 to 500 nm average particle diameter.

The lower the reflectance measured, the better the suppression of external light reflection, which means that it is advantageous to high quality image quality. In Table 11, it can be seen that in the case of Examples, the reflectance was excellent and the emission intensity was excellent.

Claims (11)

1. Alkali-soluble resins; And

   Includes; scattering particles comprising a metal oxide having an average particle diameter of 30 to 500nm,

   The alkali-soluble resin is at least one selected from the group consisting of a first cardo-based binder resin polymerized including a compound represented by the following Chemical Formula 1 and a second cardo-based binder resin polymerized including a compound represented by the following Chemical Formula 2 Photosensitive resin composition comprising:

   [Formula 1]

   

   [Formula 2]

   

   In Formula 1,

   R1 and R2 are each independently

   

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

   R3 is hydrogen or an alkyl group having 1 to 5 carbon atoms,

   In Formula 2,

   R4 and R5 are each independently

   

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

   R6 is hydrogen or an alkyl group having 1 to 5 carbon atoms.
2. The method of claim 1,

   The alkali-soluble resin is a photosensitive resin composition further comprises a cardo-based binder resin comprising at least one repeating unit of the following formula (3) and (4):

   [Formula 3]

   

   [Formula 4]

   

   In Chemical Formulas 3 and 4,

   P is each independently

   

   

   R7 and R8 are each independently hydrogen, hydroxy group, thiol group, amino group, nitro group or halogen atom,

   Ar1 is each independently a C6 to C15 aryl group,

   Y is an acid anhydride residue,

   Z is an acid 2 anhydride residue,

   A is O, S, N, Si or Se,

   a and b are each independently an integer of 1 to 6,

   n and m are each independently an integer of 0 to 30,

   Provided that n and m are not zero at the same time.
3. The method of claim 1,

   The photosensitive resin composition which further contains a blue coloring agent.
4. The method of claim 1,

   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, Photosensitive resin composition comprising at least one oxide selected from the group consisting of Ce, Ta, In and combinations thereof.
5. The method of claim 4, wherein

   The metal oxide is 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, Photosensitive resin composition comprising one or more selected from the group consisting of MgO and combinations thereof.
6. The method of claim 1,

   The alkali-soluble resin is a photosensitive resin composition further comprising an acrylic binder resin.
7. The method of claim 1,

   The scattering particles are a photosensitive resin composition that is contained in 0.1 to 50 parts by weight based on 100 parts by weight of the total photosensitive resin composition.
8. The method of claim 1,

   The cardo-based binder resin is 1 to 50 parts by weight based on 100 parts by weight of the total photosensitive resin composition.
9. The method of claim 1,

   Photopolymerizable compounds; Photopolymerization initiator; solvent; And one or more selected from the group consisting of additives.
10. A self-luminous pixel-containing color filter comprising; a blue pattern layer comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 9.
11. A color filter according to claim 10; And a light source emitting blue light.