WO2013027936A2

WO2013027936A2 - Black photosensitive resin composition and image display device having same

Info

Publication number: WO2013027936A2
Application number: PCT/KR2012/006083
Authority: WO
Inventors: 배진영; 김주성
Original assignee: 성균관대학교 산학협력단
Priority date: 2011-08-22
Filing date: 2012-07-31
Publication date: 2013-02-28
Also published as: WO2013027936A3; KR20130021128A

Abstract

Provided is a black photosensitive resin composition comprising a black organic pigment, insulating metal oxide particles, an alkali-soluble bond resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The black organic material is a photosensitive resin composition, containing a perylene black pigment, for forming an optical shield layer.

Description

Black photosensitive resin composition and image display apparatus provided with the same

The present invention relates to a black photosensitive resin composition and an image display apparatus having the same, and more particularly, to a black photosensitive resin having excellent electrical insulation and chemical resistance and having a high optical density, and an image display apparatus using the same.

Currently, the flat display market has grown to be difficult to support demand, and the center of the display is a plasma display panel (PDP), a liquid crystal display (LCD), an organic light emitting display (OLED), and a touch display market using the same. In particular, LCD is a major product in the flat display market, and is composed of a color filter, a thin film transistor, and a liquid crystal. Color filters used in color liquid crystal displays, imaging devices, and the like are usually uniformly coated by spin coating a photosensitive resin composition containing pigments corresponding to red, green, and blue colors on a substrate on which a black matrix is patterned. It is manufactured by exposing and developing the coating film formed by heat-drying, and performing heat-hardening further as needed for each color, and forming the pixel of each color. The black matrix patterned here is usually formed from a black photosensitive resin composition.

The black photosensitive resin composition is an essential material for flat display panel materials such as color filters, liquid crystal displays (LCDs), organic light emitting displays (OLEDs), and plasma display panels (PDPs). Recently, the introduction of a black column spacer, which can also serve as a column spacer capable of supporting the TFT-array layer and the color filter layer through the black matrix, in which case the even optical density required for the normal black matrix ( Optical density (OD) as well as good electrical insulation are required. However, when only carbon black is used as in the normal black matrix to form the black column spacer, the optical density is satisfactory, but electrical insulation is inferior. In addition, all of the black matrix materials using inorganic compounds did not satisfy the properties required for the black column spacer because of low insulation. In addition, in a panel in which a black matrix is formed on the TFT surface or formed on top of the color filter, electrical insulation directly affects the liquid crystal, so high insulation or low dielectric properties are required.

There are a number of basic patents relating to the black column spacer material and the low dielectric black matrix. In Japanese Laid-Open Patent Publication No. 2002-047423, in order to realize a black matrix having high blackness and insulation, cobalt oxides are contained and applied as a black pigment. In Japanese Unexamined Patent Publication No. 2007-071994, a perylene-based compound has been used as a black matrix material. In addition, Japanese Patent No. 2552391 intends to form a light shielding film using a black matrix material containing an insulating organic pigment composed of a mixed organic pigment and carbon black.

* However, in the case of cobalt oxides of Japanese Patent Laid-Open No. 2002-047423, the optical density is generally low, and the use of perylene-based organic pigments applied in Japanese Patent Laid-Open No. 2007-071994 and Japanese Patent No. 2552391 is presented. All of these methods solve the problem by increasing the total amount of pigment due to insufficient optical density in visible light, but this is insufficient to obtain satisfactory properties in chemical resistance, sensitivity, developability, pattern resolution, and the like.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a black photosensitive resin composition having low dielectric properties and a uniform optical density, and an image display apparatus using the same.

According to one aspect of the present invention, there is provided a black coating film prepared by polymerizing a black photosensitive resin composition comprising a black perylene-based organic pigment, insulating metal oxide particles, alkali-soluble binder resin, photopolymerizable compound, photopolymerization initiator and a solvent. .

According to another aspect of the present invention, a black photosensitive resin composition comprising a black perylene-based organic pigment, insulating metal oxide particles, alkali-soluble binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent is prepared by polymerizing the solvent in the total composition. With respect to 100 parts by weight of solids, except that the black organic pigment is provided with a black photosensitive resin composition containing 1 to 60 parts by weight, and the insulating particles 1 to 70 parts by weight.

According to another aspect of the present invention, perylene-based organic pigments, silica, alkali-soluble binder resin, and polymer, including per 100 parts by weight of the perylene-based organic pigment, 1 to 60 parts by weight, the silica is 1 To 70 parts by weight, the perylene-based organic pigment and the silica is provided with a black photosensitive composition having a weight ratio of 1:19 to 19: 1.

According to another aspect of the present invention, there is provided a black coating film formed on a substrate by applying and polymerizing the black photosensitive resin composition to a predetermined substrate.

According to another aspect of the present invention, there is provided an image display device including the black coating film.

According to the present invention, a black coating film using a black photosensitive resin composition having low dielectric properties and having a uniform optical density can be prepared. The black coating film has a low dielectric constant, chemical resistance, high film hardness, and can continuously maintain electrical properties and physical properties with respect to a post process.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The black photosensitive resin composition which concerns on this invention contains a black organic pigment (A1), insulating particle (A2), alkali-soluble binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). . In addition, although not particularly limited, the black photosensitive resin composition may optionally further include an additive (F).

Hereinafter, each component contained in the black photosensitive resin composition of this invention is demonstrated in detail.

Black Organic Pigment (A1)

In the present invention, a perylene-based black pigment (hereinafter simply referred to as a perylene-based pigment) is used as the black organic pigment used in the black photosensitive resin composition.

As a specific example, the perylene pigment represented by the following general formula (I) and the perylene pigment represented by the following general formula (II) are mentioned. Moreover, as a commercial item, product names K0084, K0086 (made by BASF Corporation), etc. can be used preferably.

Formula (I)

(In formula, R <^1> , R <^2> represents a C1-C3 alkylene group each independently, and R <^3> , R <^4> represents a hydrogen atom, a hydroxyl group, a methoxy group, or an acetyl group each independently.)

General formula (II)

(In formula, R <^5> , R <^6> represents a C1-C7 alkylene group each independently.)

As a compound represented by the said General formula (I) and the compound represented by the said General formula (II), the method of Unexamined-Japanese-Patent No. 62-1753 and Unexamined-Japanese-Patent No. 63-26784 is used, for example. Can be synthesized. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amine are used as a raw material, and heat reaction is performed in water or an organic solvent. And the target object can be obtained by reprecipitating the obtained preparation in sulfuric acid or recrystallizing in water, an organic solvent, or these mixed solvent.

In this invention, a perylene pigment may be used individually by 1 type and may use 2 or more types together.

Moreover, in order to make a perylene pigment into a dispersed state in the said black photosensitive resin composition, it is preferable that the average particle diameter of a perylene pigment is 10-100000 nm.

As for content of the perylene pigment in the photosensitive resin composition for light-shielding layer formation of this invention, 50-300 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble binder resin. More preferable range is 100-250 mass parts. By making content of a perylene pigment more than the lower limit of the said range, favorable light-shielding property is obtained. Moreover, it is preferable to set it below the upper limit of the said range in order to prevent exposure defect or hardening defect.

Moreover, you may adjust color tone etc. using the pigment | dye of black, red, blue, green, sulfur, purple other than black organic pigment (A1) together. The other pigment | dye can use a well-known thing suitably.

The black organic pigment resin composition may further include an additive such as a dispersant. The dispersant serves to control agglomeration between the black organic particles. The dispersant may be one containing a hydrophilic group and a hydrophobic group that can control the aggregation between the black organic particles. The surface of the black organic particle | grains which comprise black organic particle | grain resin composition can also be used beforehand treating with the dispersing agent. The dispersant may be a urethane-based dispersant, an acrylic dispersant or an epoxy dispersant, but is not limited thereto. Examples of the urethane-based dispersant include those selected from the group consisting of disperbyk 2150 (manufactured by BYK chemie), disperbyk 164 (manufactured by BYK chemie), disperbyk 163 (manufactured by BYK chemie) and combinations thereof. Examples of the acrylic dispersant include disperbyk 2070 (manufactured by BYK chemie).

Insulating Particles (A2)

As the insulating particles A2, inorganic metal oxide particles such as silica, alumina, titania, and zirconia may be used. The said insulating particle (A2) can be used individually or in combination of 2 or more types, It is preferable to use what can provide the outstanding electrical insulation, mixing uniformly with a black organic pigment (A1).

Preferred examples of the insulating particles (A2) include silica or alumina particles. The silica (SiO ₂ ) or alumina (Al ₂ O ₃ ) used may be substantially spherical, sub-micron sized particles dispersed in an aqueous or other solvent medium. The silica or alumina particles used in the present invention may have a size of less than 1 micrometer with an average particle diameter of 10 to 100 nm, preferably 10 to 50 nm. Average particle size can be determined using transmission electron microscopy. In addition, silica or alumina particles generally have a surface area of greater than about 100 m ² / gram. For maximum improvement in shear value, the particles preferably have a narrow particle size distribution, ie the polydispersity may be 2.0 or less, preferably 1.5 or less. If desired, smaller amounts of larger silica or alumina particles may be added, but such addition may not contribute to an increase in shear value.

Specific examples of the silica include, but are not limited to, nano silica (AEROSIL 200, TT 600; manufactured by Degussa) and hydrophobic nano silica (AEROSIL R972; manufactured by Degussa).

In the case of using the insulating particles A2, the shape of the particles is not limited. The insulating particles may preferably have a shape with an average particle diameter of 0.1 μm or less, which can be observed by an electron microscope. The surface of the insulating particles may be treated with a silane coupling agent or the like. In this case, compatibility with the binder resin and adhesive properties can be improved.

In addition, in order to ensure better electrical insulation and optical density, when the sum of the solid content of the black organic pigment (A1) and the insulating particles (A2) is 100 parts by weight, the ratio of the two materials (A1) and (A2) The black organic pigment (A1) may be contained in an amount of 5 to 95 parts by weight based on 100 parts by weight of the solid content, and the insulating particles (A2) may be contained in an amount of 5 to 95 parts by weight based on 100 parts by weight of the solid content.

The black organic pigment (A1) may contain 10 to 70 parts by weight based on 100 parts by weight of solids in the black photosensitive resin composition. If the content of the black organic pigment (A1) is less than 10 parts by weight, the optical density is not sufficient, if more than 70 parts by weight, the optical density is sufficient, but pattern formation may be difficult.

In addition, the insulating particles (A2) may contain 1 to 70 parts by weight based on 100 parts by weight of solids in the black photosensitive resin composition. If the content of the insulating particles (A2) is less than 1 part by weight, the insulation is not sufficient, if more than 70 parts by weight, the insulation is sufficient, but pattern formation may be difficult.

Alkali-Soluble Binder Resin (B)

The alkali-soluble binder resin (B) is applicable to those commonly used in the art, in particular, it is preferable that the alkali-soluble binder resin (B) is a copolymer of a compound having an unsaturated carboxyl group and other monomers copolymerizable therewith.

The compound having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and each compound can be used alone or in combination of two or more thereof.

Specific examples of the compound having an unsaturated carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of the dicarboxylic acids; Mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2- Carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, or a mixture thereof. Among the compounds having an unsaturated carboxyl group exemplified above, acrylic acid and methacrylic acid are preferred because of excellent copolymerization reactivity and solubility in a developing solution.

Other monomers copolymerizable with the monomer having a carboxyl group are monomers having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylate compounds such as acrylates; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3- methacryloxyethyl oxetane, etc. And unsaturated oxetane carboxylate compounds.

In addition, the alkali-soluble binder resin may be used a cardo resin generally used in the art.

The cardo-based resin is 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3-methylphenyl) -2-benzofuran -1 (3H) -one, 3,3-bis (4-hydroxy-2,5-dimethylphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy- 1-naphthyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-5-isopropyl-2-methylphenyl) -2-benzofuran-1 (3H) -one , 3,3-bis (3,5-dibromo-4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3,5-di Iodinephenyl) -2-benzofuran-1 (3H) -one, 9,9-bis (4-hydroxyphenyl) -10-anthrone, 1,2-bis (4-carboxyphenyl) carbonan, 1, 7-bis (4-carboxyphenyl) carbonan, 2-bis (4-carboxyphenyl) -N-phenylphthalimidine, 3,3-bis (4'-carboxyphenyl) phthalide, 9,10-bis- (4-aminophenyl) -anthracene, anthrone dianiline, aniline phthalein and the like. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone and bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxy Phenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorofetyl) methane and bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3- Methylphenyl) propane and 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-di Butylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3- Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis ( 4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethyl Phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene It may be obtained by polymerizing a compound containing at least one monomer.

The alkali-soluble binder resin (B) may be included in 5 to 60 parts by weight, preferably 10 to 40 parts by weight based on 100 parts by weight of solids in the black photosensitive resin composition. When the alkali-soluble binder resin (B) is within the content range on the basis of the above standard, the formation of a pattern is possible, and the resolution and the residual film ratio are improved.

Photopolymerizable Compound (C)

The said photopolymerizable compound (C) 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-vinylpyrroly Money, etc.

Specific examples of the bifunctional monomers 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, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound (C) may be used in the range of 5 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the alkali-soluble binder resin (B) and the photopolymerizable compound (C) based on solid content. Can be. If the photopolymerizable compound (C) is in the range of 5 to 80 parts by weight based on the above criteria, the pattern characteristic becomes good, and therefore it is preferable.

Photopolymerization Initiator (D)

Although the said photoinitiator (D) is not restrict | limited, It is preferable to use at least 1 sort (s) of compound chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound.

As said triazine type compound, it is 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-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

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-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned.

In addition, the acetophenone-based compound may be a compound represented by the following formula (1).

In Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a benzyl which may be substituted by an alkyl group having 1 to 12 carbon atoms. The naphthyl group which may be substituted by the group or the C1-C12 alkyl group is shown.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole can be preferably used.

As said oxime compound, the compound etc. which are represented by following General formula (2)-4 are mentioned, for example.

Moreover, in addition to the photoinitiator mentioned above, the other photoinitiator etc. which are normally used in this field can also be used together if it is a grade which does not impair the effect of this invention. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, a polyfunctional thiol compound, etc. are mentioned, for example. These can be used individually or in combination of 2 types or more, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, and pentaerythritol tetrakis-3. Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

According to this invention, you may use combining the photoinitiator (D) with a photoinitiator adjuvant (D-1). When using a photoinitiator (D-1) together with a photoinitiator (D), since the black photosensitive resin composition containing these is more sensitive, productivity at the time of forming a black matrix or a black column spacer using this is preferable. .

As the photopolymerization initiation assistant (D-1), one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), Aromatic amine compounds, such as 4,4'-bis (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used. Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the photopolymerization initiator (D) is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble binder resin (B) and the photopolymerizable compound (C) based on the solid content. In addition, the content of the photopolymerization initiation assistant (D-1) is 0.1 to 50 parts by weight, preferably 1 to 1, based on 100 parts by weight of the total amount of the alkali-soluble binder resin (B) and the photopolymerizable compound (C) based on the solid content. 40 parts by weight. When the content of the photopolymerization initiator (D) is in the above range on the basis of the above criteria, the black photosensitive resin composition is highly sensitive, and thus the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion become good. desirable. Moreover, since the sensitivity of a black photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, when the usage-amount of a photoinitiator auxiliary (D-1) exists in said range on the said reference | standard.

Solvent (E)

The solvent (E) is not particularly limited, and various organic solvents commonly used in the art may be used.

Specific examples of the solvent (E) 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, and diethylene. Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol Alkoxy alkyl acetates, such as alkylene glycol alkyl ether acetates, such as a monomethyl ether acetate, a propylene glycol monoethyl ether acetate, and a propylene glycol monopropyl ether acetate, a methoxy butyl acetate, and a methoxy pentyl acetate,

Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene Alcohols such as glycol and glycerin, esters such as 3-ethoxy propionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Ester, such as ethyl and 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl propionate etc. are mentioned.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (E) is 20-90 weight part with respect to 100 weight part of all black photosensitive resin compositions containing it, Preferably it is 60-85 weight part. When content of the said solvent (E) is the range of 20-90 weight part on the said reference | standard, it applied with the coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (it may be called a die coater), and inkjet. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

The black photosensitive resin composition of this invention can also use together the additive (F), such as another high molecular compound, a hardening | curing agent, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the other high molecular compound include thermosetting 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 mentioned.

The said hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Specific examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a noblock type epoxy resin, other aromatic epoxy resins, and an alicyclic epoxy resin. , Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.).

The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.

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 phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethylene Imine, etc .; KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink Chemical Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), Solsperth (SOLSPERSE) (made by Lubrisol), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), Disperbyk-series (made by BYK-chemie), etc. are mentioned.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

Each of the adhesion promoters may be used alone or in combination of two or more, and 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the solid content of the black photosensitive resin composition.

Specific examples of the antioxidant include hindered phenols such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

As a specific example of the said ultraviolet absorber, 2- (3-tert- butyl- 2-hydroxy-5- methylphenyl) -5-chlorobenzothiazole, an alkoxy benzophenone, etc. are mentioned.

As a specific example of the said aggregation inhibitor, sodium polyacrylate is mentioned.

The black photosensitive resin composition of this invention can be manufactured by the following method, for example.

The black organic pigment (A1) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the black organic pigment becomes about 0.15 µm or less. At this time, a pigment dispersant is used as needed, and some or all of alkali-soluble binder resin (B) may be mix | blended. The dispersion liquid of the obtained black organic pigment (A1) is mixed with the remainder of the solvent (E) in a fixed ratio using a stirrer or the like. After adding the insulating particle (A2), the remainder of alkali-soluble binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and the additive (F) as needed to this liquid mixture, it is further added as needed. A solvent is further added so that it may become a predetermined concentration, and a desired black photosensitive resin composition is obtained.

According to one embodiment of the present invention, when the above-described black photosensitive resin composition is applied to a predetermined substrate and polymerized, a black coating film may be formed on the substrate. After application to a substrate through a known coating method such as spin coating, a polymer is formed in the black photosensitive resin composition by heat or light, and the solvent is removed to cure to a solid phase. The black coating film thus formed contains inorganic oxide particles, thereby providing excellent chemical resistance, low electrical insulation, and high surface hardness.

The image display device to which the black photosensitive resin composition is applied may have improved reflectivity and contrast ratio, thereby improving visibility of the screen, and since inorganic oxide particles are included in the film, chemical resistance, insulation, and durability are high.

As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and 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 modifications within the meaning and range equivalent to the claims. In addition, the number described in the table | surface of a following example and a comparative example shows a weight part.

Of the components shown in Table 1 below, 60 parts by weight of a black organic pigment (A1), a dispersant (F1, F2), and a solvent (E1) were previously mixed into a container, followed by stirring for 3 minutes using a homogenizer. Dispersion was performed by repeating the process of performing ultrasonication for 3 minutes three times, and after dispersing was completed, 20 parts by weight of the remaining amount of the solvent (E1) were added to prepare black organic pigment dispersions BK 1 to 4.

Table 1

Black Organic Pigment Dispersion (BK)		Preparation Example 1 (BK1)	Preparation Example 2 (BK2)	Preparation Example 3 (BK3)	Preparation Example 4 (BK4)
Black Organic Pigment (A1)	PBK	16	16	16	16
Pigment Dispersant (F1)		4	3	2	0
Pigment Dispersant (F2)		0	One	2	4
Solvent (E1)		80	80	80	80
Viscosity (cp @ 20 rpm)		2.7	2.9	2.9	3.0
Particle size (nm)		70	80	80	70

Black Organic Pigment (A1)

-PBK: Perylene Organic Pigment (K0086, manufactured by BASF)

Dispersant (F1): Disperbyk-2150 (manufactured by BYK chemi)

Dispersant (F2): Disperbyk-163 (manufactured by BYK chemi)

Solvent (E1): propylene glycol monomethyl ether acetate

Each component of the following Table 2 was mixed and the black photosensitive resin composition was obtained.

TABLE 2

division	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2	Comparative Example 3
Black Organic Pigment Dispersion (BK)	BK134	BK234	BK334	BK434	BK134	BK133.04	BK138.76	BK238.76	BK438.76
Insulating Particles (Silica) (A2)	4.76	4.76	4.76	4.76	4.76	5.72
Alkali-soluble binder resin (B)	Cardo resin (WR-101, product made by Adeka Corporation) 4.2
Photopolymerizable Compound (C)	Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 4.2
Photopolymerization Initiator (D)	Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Cibasa Manufacture) 1.0
Solvent (E)	Propylene Glycol Monomethyl Ether Acetate
Additive (F1)	Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) 0.5
Additive (F2)	3-methacryloxypropyltrimethoxysilane0.02

Experimental Example

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the black photosensitive resin composition which concerns on the said Example and a comparative example was exposed by 100 mJ / cm <2> exposure amount (365 nm), and spin-coating so that the film thickness after baking may be 3.0 micrometer when the image development process is skipped. Then, it was pre-dried at 100 degreeC for 3 minutes in the clean oven. After cooling, the board | substrate to which this black photosensitive resin composition was apply | coated was irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Then, it baked after 30 minutes at 220 degreeC.

1. Optical Density Measurement

The optical density in 550 nm wavelength was measured for the black board | substrate produced by the said method using OSP-200 (made by Olympus). The measured results are shown in Table 3. Optical density (OD) = -Log ₁₀ T (T is 550nm transmittance)

○: optical density is 3 or more

△: optical density is 2 or more but less than 3

X: optical density is 2 or less

2. Measurement of dielectric constant

An aluminum electrode was formed on the black substrate made by the above method using an aluminum vacuum deposition apparatus and a mask. At this time, the aluminum electrode was deposited in a thickness of 0.075 ± 0.025 μm on a black layer and an uncoated layer (ITO electrode) in a 5 mm diameter circular shape.

Capacitance when an alternating voltage of 1 to 100 kHz, 1 V was applied to the aluminum electrode on the coating layer of the deposited specimen and the aluminum electrode of the non-coat layer using a capacitance meter (trade name LCR meter 4284A, Agilnet, Inc.). It measured, and the dielectric constant was computed from the value, and is shown in Table 3.

○: relative dielectric constant is 5 or less

△: relative dielectric constant is 5 or more and 8 or less

X: relative dielectric constant is 8 or more

TABLE 3

division	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Comparative Example 1	Comparative Example 2	Comparative Example 3
OD	○	○	○	○	○	○	○	○	○
Relative dielectric constant	○	○	○	○	○	○	×	×	×

As shown in Table 3 above, the black photosensitive resin composition of the embodiment comprising a perylene-based pigment, which is a black organic pigment, and silica, which is an insulating particle, and which is included within a preferred range of the present invention, has excellent optical insulation while having a uniform optical density. It can be seen that a black matrix or black column spacer is obtained. However, in the case of Comparative Examples 1 to 3 without combining the insulating particles, it can be seen that the relative dielectric constant is not good compared to Examples 1 to 6 used by combining both the black organic pigment and the insulating particles.

According to the present invention, a black coating film using a black photosensitive resin composition having low dielectric properties and having a uniform optical density may be manufactured. The black coating film has a low dielectric constant, chemical resistance, high film hardness, and can continuously maintain electrical properties and physical properties with respect to a post process.

Claims

Black photosensitive resin composition containing a black perylene-type organic pigment, insulating metal oxide particle, alkali-soluble binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The method of claim 1,

The insulating metal oxide particles are black photosensitive resin composition comprising one or more selected from the group consisting of silica, alumina, titania, and zirconia.
The method of claim 1,

The insulating particles are black photosensitive resin composition containing silica or alumina.
The method of claim 1,

The black perylene-based organic pigment is 5 to 95 parts by weight, the insulating particles are 5 to 95 parts by weight, and the black perylene-based based on 100 parts by weight of the total solids of the black perylene-based organic pigment and the insulating metal oxide particles. Solid of the organic pigment and the insulating particles is a black photosensitive resin composition containing 5 to 95 parts by weight of the total composition.
The method of claim 1,

The solvent is a black photosensitive resin composition containing 10 to 90 parts by weight based on 100 parts by weight of the total composition.
It is prepared by polymerizing a black photosensitive resin composition comprising a black perylene-based organic pigment, insulating metal oxide particles, alkali-soluble binder resin, photopolymerizable compound, photopolymerization initiator and a solvent,

A black photosensitive resin composition containing 10 to 70 parts by weight of the black perylene-based organic pigment, and 1 to 70 parts by weight of the insulating particles, based on 100 parts by weight of the solid content excluding the solvent in the whole composition.
The method of claim 3, wherein

The black photosensitive resin composition whose average particle diameter of the said silica or alumina is 10-100 nm, and polydispersity is 2.0 or less.
The method of claim 6,

The black perylene-based organic pigment and the insulating metal oxide particles have a black photosensitive resin composition having a weight ratio of 1:19 to 19: 1.
The method of claim 3,

The insulating metal oxide particles are black photosensitive resin composition treated with a silane coupling agent.
Perylene-based organic pigments, silica, alkali-soluble binder resins, and polymers,

10 parts by weight to 70 parts by weight of the perylene-based organic pigment and 1 to 70 parts by weight of the silica, and the perylene-based organic pigment and the silica has a weight ratio of 1:19 to 19: 1. Black photosensitive resin composition.
The method according to any one of claims 1 to 10,

The black coating film formed on the board | substrate by apply | coating and polymerizing the said black photosensitive resin composition to a predetermined board | substrate.
An image display device comprising the black coating film of claim 11.