TWI716262B - Resin composition, cured film and black matrix - Google Patents

Abstract

A resin composition, a cured film and a black matrix are provided. The resin composition includes an epoxy resin (A), a black coloring agent (B), a photoinitiator (C), a thermal acid generator (D), a polymerizable monomer (E) and a solvent (F). The thermal acid generator (D) includes hexafluoroonium salt. The polymerizable monomer (E) includes a photopolymerizable monomer (E-1), an epoxy resin monomer (E-2) or the combination thereof. Based on a total usage amount of the polymerizable monomer (E) as 100 parts by weight, a usage amount of the epoxy resin monomer (E-2) is 15 to 70 parts by weight.

Description

Resin composition, cured film and black matrix

The present invention relates to a resin composition, and more particularly to a resin composition suitable for a black matrix, a cured film and a black matrix.

With the vigorous development of liquid crystal display device technology, in order to improve the contrast and display quality of the liquid crystal display device, a black matrix is usually placed in the liquid crystal display device to prevent the drop in contrast and color purity caused by light leakage between pixels. , Or prevent problems such as noise and poor image quality. However, the black matrix currently used has problems such as insufficient hardness, poor developability, poor patterning, or poor light-shielding properties. For example, the current black matrix may cause damage such as scratches on its surface or may cause light leakage between pixels, thereby affecting the performance of the device using the black matrix.

In view of this, the present invention provides a resin composition, cured film, and black matrix that can be formed with good light-shielding properties, hardness, resolution, and reactivity.

A resin composition of the present invention includes epoxy resin (A), black colorant (B), photoinitiator (C), thermal acid generator (D), polymerizable monomer (E) and solvent (F) . The thermal acid generator (D) includes hexafluoroonium salt. The polymerizable monomer (E) includes a photopolymerizable monomer (E-1), an epoxy resin monomer (E-2), or a combination thereof. Based on the total amount of the polymerizable monomer (E) used is 100 parts by weight, the amount of the epoxy resin monomer (E-2) used is 15 to 70 parts by weight.

In an embodiment of the present invention, the structural unit contained in the aforementioned epoxy resin (A) includes an epoxy-containing structural unit, and the epoxy-containing structural unit has a double bond.

式（a-1），*表示鍵結位置。 In an embodiment of the present invention, the above-mentioned epoxy-containing structural unit includes a structural unit represented by the following formula (a-1):

Formula (a-1), * represents the bonding position.

In an embodiment of the present invention, the structural unit contained in the aforementioned epoxy resin (A) further includes a structural unit having an ethylenically unsaturated group and a structural unit having an aryl group.

式（a-2），

式（a-3），*表示鍵結位置。 In an embodiment of the present invention, the aforementioned structural unit having an ethylenically unsaturated group includes at least one of the structural units represented by the following formula (a-2) and formula (a-3):

Formula (a-2),

Formula (a-3), * represents the bonding position.

式（a-4），

式（a-5），

式（a-6），*表示鍵結位置。 In an embodiment of the present invention, the aforementioned structural unit having an aryl group includes at least one of the structural units represented by the following formula (a-4), formula (a-5), and formula (a-6):

Formula (a-4),

Formula (a-5),

Formula (a-6), * represents the bonding position.

In an embodiment of the present invention, the aforementioned photoinitiator (C) includes at least one selected from the group consisting of oxime ester derivatives, halogenated hydrocarbon derivatives and hydrocarbyl acetophenone.

In an embodiment of the present invention, the above-mentioned photopolymerizable monomer (E-1) has an ethylenically unsaturated group.

In an embodiment of the present invention, the above-mentioned polymerizable monomer (E) further includes a silane monomer (E-3) having an epoxy group.

In an embodiment of the present invention, the aforementioned solvent (F) includes at least one selected from the group consisting of propylene glycol monomethyl ether acetate, 3-ethoxy ethyl propionate, and dipropylene glycol methyl ether acetate. One kind.

In an embodiment of the present invention, based on the usage amount of the epoxy resin (A) being 100 parts by weight, the usage amount of the thermal acid generator (D) is 80 parts by weight to 100 parts by weight.

In an embodiment of the present invention, based on the amount of epoxy resin (A) used is 100 parts by weight, the amount of black colorant (B) used is 230 to 250 parts by weight, and the amount of photoinitiator (C) is The usage amount is 80 parts by weight to 100 parts by weight, the usage amount of the polymerizable monomer (E) is 305 parts by weight to 325 parts by weight, and the usage amount of the solvent (F) is 1945 parts by weight to 1965 parts by weight.

A cured film of the present invention is formed of the above-mentioned resin composition.

A black matrix of the present invention is the above-mentioned cured film.

Based on the above, the resin composition of the present invention uses a specific thermal acid generator (D) and an epoxy resin monomer (E-2), and the total amount based on the polymerizable monomer (E) is 100 parts by weight. The amount of the oxygen resin monomer (E-2) used is 15 to 70 parts by weight. As a result, when the resin composition is used to form a cured film, the cured film can have good light-shielding properties, hardness, resolution, and reactivity, and is suitable for black matrices.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the following specific embodiments are described in detail as follows.

> Resin composition >

The present invention provides a resin composition comprising epoxy resin (A), black colorant (B), photoinitiator (C), thermal acid generator (D), polymerizable monomer (E) and solvent (F) ). In addition, the resin composition of the present invention may further include additives (G) such as a leveling agent as necessary. Hereinafter, the above-mentioned various components will be described in detail.

Hereinafter, it is explained that acrylic acid and/or methacrylic acid are represented by (meth)acrylic acid, and acrylate and/or methacrylate are represented by (meth)acrylate. Epoxy resin ( A )

The structural unit contained in the epoxy resin (A) includes an epoxy group-containing structural unit, and the epoxy group-containing structural unit has a double bond.

式（a-1） 式（a-1）中，*表示鍵結位置。 For example, the epoxy group-containing structural unit may be derived from glycidyl (meth)acrylate, 3,4-epoxycyclohexane (meth)acrylate, 3,4-cyclic (meth)acrylate Monomers such as methyl oxycyclohexane or other suitable compounds. The epoxy group-containing structural unit is preferably derived from glycidyl (meth)acrylate, and the epoxy group-containing structural unit produced therefrom may include a structural unit represented by the following formula (a-1).

Formula (a-1) In formula (a-1), * represents the bonding position.

The structural unit contained in the epoxy resin (A) may further include a structural unit having an ethylenically unsaturated group and a structural unit having an aryl group.

式（a-2）

式（a-3） 式（a-2）及式（a-3）中，*表示鍵結位置。 For example, the structural unit having an ethylenically unsaturated group may be derived from monomers such as (meth)acrylic acid, methyl (meth)acrylate, n-alkyl (meth)acrylate, or other suitable compounds. The structural unit having an ethylenically unsaturated group is preferably derived from at least one of (meth)acrylic acid and methyl (meth)acrylate, and the structural unit having an ethylenically unsaturated group produced therefrom may include the following At least one of the structural units represented by formula (a-2) and formula (a-3) is described.

Formula (a-2)

Formula (a-3) In formula (a-2) and formula (a-3), * represents the bonding position.

式（a-4）

式（a-5）

式（a-6） 式（a-4）、式（a-5）及式（a-6）中，*表示鍵結位置。 For example, the structural unit having an aryl group may be derived from monomers such as benzyl (meth)acrylate, styrene, N-phenylmaleimide or other suitable compounds. The structural unit having an aryl group is preferably derived from at least one of benzyl methacrylate, styrene, and N-phenylmaleimide, and the structural unit having an aryl group produced therefrom may include the following At least one of the structural units represented by formula (a-4), formula (a-5), and formula (a-6).

Formula (a-4)

Formula (a-5)

Formula (a-6) In formula (a-4), formula (a-5) and formula (a-6), * represents the bonding position.

In addition, without affecting the efficacy of the present invention, the structural unit contained in the epoxy resin (A) may further include other structural units. The other structural unit is not particularly limited, as long as it is different from the epoxy group-containing structural unit, the structural unit having an ethylenically unsaturated group, and the structural unit having an aryl group.

For example, the epoxy resin (A) can be one type of epoxy resin or a combination of multiple types of epoxy resins. For example, the epoxy resin (A) may be the following epoxy resin (A-1), the following epoxy resin (A-2), or a combination thereof.

The structural unit contained in the epoxy resin (A-1) is the structural unit represented by the formula (a-1), the structural unit represented by the formula (a-2), the structural unit represented by the formula (a-4), and the formula (a -5) The structural unit indicated. In addition, the structural unit contained in the epoxy resin (A-2) is a structural unit represented by formula (a-1), a structural unit represented by formula (a-2), a structural unit represented by formula (a-3), and The structural unit represented by (a-5) and the structural unit represented by formula (a-6).

The weight average molecular weight of the epoxy resin (A) can be measured by Gel Permeation Chromatography (GPC). The weight average molecular weight of the epoxy resin (A) may be 5,000 to 25,000, preferably 7,000 to 23,000, and more preferably 10,000 to 20,000. Black colorant ( B )

The black colorant (B) is not particularly limited, and an appropriate black colorant can be selected according to requirements. For example, the black colorant (B) may be composed of one or more organic black pigments, inorganic black pigments or a combination thereof through grinding and dispersion. Organic black pigments may include internal amine organic black, RGB black, RVB black, and the like. The inorganic black pigment may include nigrosine, perylene black, titanium black, cyanine black, lignin black, carbon black, or a combination thereof. RGB black, RVB black, etc. indicate a pigment that shows black by mixing at least two color pigments among red pigments, green pigments, blue pigments, violet pigments, yellow pigments, and violet pigments. The black colorant (B) preferably includes carbon black.

Based on 100 parts by weight of epoxy resin (A) and 200 parts by weight to 300 parts by weight of black colorant (B), preferably 210 parts by weight to 290 parts by weight, more preferably 220 parts by weight To 280 parts by weight.

When the resin composition contains the black coloring agent (B), the cured film formed by the resin composition can have light-shielding properties, and it is suitable for a black matrix. At the same time, when the usage amount of the black colorant (B) falls within the above range, the cured film formed by the resin composition can have good light-shielding properties (for example, the optical density (OD) is greater than 2.5). Photoinitiator ( C )

The photoinitiator (C) includes at least one selected from the group consisting of oxime ester derivatives, halogenated hydrocarbon derivatives and hydrocarbyl acetophenones, and preferably includes oxime ester derivatives.

式（c-1）

式（c-2） The oxime ester derivative may include a compound represented by the following formula (c-1), a compound represented by the formula (c-2), 1-[9-ethyl-6-[2-methyl-4-[ (Tetrahydro-2-furyl)methoxy]benzyl]-9H-carbazol-3-yl]-1-(O-acetoxime)ethanone or other suitable oxime ester derivatives. The oxime ester derivative preferably includes a compound represented by the following formula (c-2). The oxime ester derivative may be used alone or in combination of multiple types.

Formula (c-1)

Formula (c-2)

The halogenated hydrocarbon derivatives may include chlorinated methane, vinyl chloride, chlorobenzene or other suitable halogenated hydrocarbon derivatives. The halogenated hydrocarbon derivatives may be used alone or in combination of multiple types.

The hydrocarbyl acetophenone may include p-hydrocarbyl acetophenone, o-hydrocarbyl acetophenone, or other suitable hydrocarbyl acetophenone. The hydrocarbyl acetophenone may be used alone or in combination of multiple types.

Based on 100 parts by weight of epoxy resin (A) and 20 parts by weight to 140 parts by weight of photoinitiator (C), preferably 40 parts by weight to 120 parts by weight, more preferably 60 parts by weight Parts to 100 parts by weight.

When the resin composition includes the photoinitiator (C), the resin composition can have good patterning ability. At the same time, when the usage amount of the photoinitiator (C) falls within the above range, a resin composition with better patterning ability can be obtained. In addition, if the resin composition does not include the photoinitiator (C), the resin composition cannot form a cured film. Thermal acid generator ( D )

The thermal acid generator (D) includes a hexafluoroonium salt or other suitable thermal acid generator, and preferably includes a hexafluoroonium salt.

式（d-1） The hexafluoroonium salt may include a compound represented by the following formula (d-1), triarylsulfonium hexafluoroantimony salt, 4,4'-xylyl iodonium hexafluorophosphate, bis(4-tertiary butylbenzene) ) Iodohexafluorophosphate, 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate, diaryliodonium hexafluorophosphate (for example, xylyl iodonium hexafluorophosphate), 4-isopropyl-4'-methyldiphenyl iodide tetrakis (pentafluorophenyl) borate, 4,4'-xylyl iodonium hexafluorophosphate, (sulfur-di-4,1- Phenyl) diphenyl sulfonium hexafluorophosphate, hexafluorophosphate (1-) diphenyl [(phenylthio) phenyl] sulfonate, diphenyl [4-(phenyl thio) benzene Yl]-hexafluoroantimonate or other suitable hexafluoroonium salts. The hexafluoroonium salt preferably includes a compound represented by the following formula (d-1). The hexafluoroonium salt may be used alone or in combination of multiple types.

Formula (d-1)

When the resin composition includes the thermal acid generator (D), the thermal acid generator (D) can be used as, for example, a crosslinking accelerator to obtain a resin composition with good hardness and the resulting resin composition with good hardness, resolution and Reactive hardened film.

Based on 100 parts by weight of epoxy resin (A) and 20 parts by weight to 140 parts by weight of thermal acid generator (D), preferably 40 parts by weight to 120 parts by weight, more preferably 60 parts by weight Parts to 100 parts by weight. Polymerizable monomer ( E )

The polymerizable monomer (E) includes a photopolymerizable monomer (E-1), an epoxy resin monomer (E-2), or a combination thereof.

For example, the photopolymerizable monomer (E-1) may have an ethylenically unsaturated group. The photopolymerizable monomer having an ethylenically unsaturated group (E-1) may include a polyfunctional monomer having at least one ethylenically unsaturated group, for example, may include a compound formed from an aliphatic polyhydroxy compound and an unsaturated carboxylic acid Esters, esters formed by aromatic polyhydroxy compounds and unsaturated carboxylic acids, or esters of polyhydroxy compounds (such as aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc.) with unsaturated carboxylic acids and polybasic carboxylic acids The ester formed by the chemical reaction. However, the present invention is not limited to this, and the photopolymerizable monomer (E-1) may also include other suitable monomers.

The ester formed by aliphatic polyhydroxy compounds and unsaturated carboxylic acids may include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, The acrylates of pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate or other aliphatic polyhydroxy compound, preferably Including dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate. The ester formed by an aromatic polyhydroxy compound and an unsaturated carboxylic acid may include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate (Meth)acrylates of esters, pyrogallol triacrylate or other aromatic polyhydroxy compounds. The photopolymerizable monomer (E-1) may be used alone or in combination of multiple monomers.

Based on the total usage amount of the polymerizable monomer (E) being 100 parts by weight, the usage amount of the photopolymerizable monomer (E-1) is 20 parts by weight to 100 parts by weight, preferably 30 parts by weight to 90 parts by weight, More preferably, it is 40 to 80 parts by weight.

Epoxy resin monomer (E-2) may include chloromethyl oxirane, glycidyl-terminated bisphenol A epichlorohydrin, 4,4-(1-methylethyl indenyl) dicycloethyl Diglyceryl ether ester, 1,1-bis(2,3-epoxypropoxy)phenylethane, 2,2-bis[4-(2-hydroxy-3-methacryloyl)phenyl] Propane, 4,6-bis(1-adamantane)-1,3-diepoxypropaneoxybenzene, 4-epoxypropaneoxycarbazole, 3-[(p-acetamido)phenoxy] -1,2-propylene oxide, bisphenol A diglycidyl ether, 1-(4-benzyloxyphenoxy)-2,3-propylene oxide or other epoxy resin monomers, preferably including bisphenol Phenol A diglycidyl ether. The epoxy equivalent of the epoxy resin monomer (E-2) is 100 grams/equivalent (g/eq) to 300 grams/equivalent, preferably 120 grams/equivalent to 280 grams/equivalent, more preferably 140 grams/equivalent To 260 g/equivalent. The epoxy resin monomer (E-2) can be used alone or in combination with multiple monomers.

Based on the total usage amount of the polymerizable monomer (E) being 100 parts by weight, the usage amount of the epoxy resin monomer (E-2) is 15 parts by weight to 70 parts by weight, preferably 20 parts by weight to 65 parts by weight, More preferably, it is 25 to 60 parts by weight.

When the resin composition includes the epoxy resin monomer (E-2) and the usage amount falls within the above range, the epoxy resin monomer (E-2) can make the resin composition have good hardness and can form a good The hardness, resolution and reactivity of the cured film.

In this embodiment, the polymerizable monomer (E) may further include a silane monomer (E-3) having an epoxy group. The epoxy resin monomer (E-2) is a monomer other than the siloxane monomer (E-3) having an epoxy group. In addition, in other embodiments, the polymerizable monomer (E) may further include other suitable monomers.

Silane monomers (E-3) with epoxy groups may include glycidyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxy Silane, 3-glycidoxypropyl dimethylmethoxysilane, 1-(3-glycidoxypropyl)-1,1,3,3,3-pentaethoxy-1,3 -Disiloxane, 3-glycidyl ether propyl heptamethyl cyclotetrasiloxane, (3-glycidyl ether oxypropyl) methyl-dimethyl copolysiloxane, monoglycidyl ether propyl seal Terminated polydimethylsiloxane, tertiary butyldimethylsilyl glycidyl ether, mono(2,3-epoxy)propyl ether terminated polydimethylsiloxane or other suitable monomers, Preferably, it includes glycidyl trimethoxysilane. The epoxy-containing silane monomer (E-3) can be used alone or in combination with multiple monomers.

Based on 100 parts by weight of epoxy resin (A) and 200 parts by weight to 400 parts by weight of polymerizable monomer (E), preferably 220 parts by weight to 380 parts by weight, more preferably 240 parts by weight Parts to 360 parts by weight. Solvent ( F )

The solvent (F) is not particularly limited, and an appropriate solvent can be selected according to requirements. The solvent (F) preferably includes selected from propylene glycol monomethyl ether acetate (PGMEA), ethyl 3-ethoxypropionate (ethyl 3-ethoxypropionate, EEP) and dipropylene glycol monomethyl ether acetate (PGMEA). At least one of the esters (di (propylene glycol) methyl ether acetate, DPMA) is composed of at least one kind, and more preferably includes propylene glycol monomethyl ether acetate. The solvent (F) can be used alone or in combination of multiple types.

Based on the amount of epoxy resin (A) used is 100 parts by weight, the amount of solvent (F) used is 1500 parts by weight to 2500 parts by weight, preferably 1600 parts by weight to 2400 parts by weight, more preferably 1700 parts by weight to 2300 parts by weight Parts by weight. Additives ( G )

The resin composition may further include an additive (G). In this embodiment, the additive (G) may include a leveling agent. There are no special restrictions on the leveling agent, and an appropriate leveling agent can be selected according to requirements. For example, the leveling agent may include alkoxysilane compounds or other suitable leveling agents. Alkoxysilane compounds may include 3-glycidyloxypropyl trimethoxysilane ((3-glycidyloxypropyl)trimethoxysilane), 1,1,3,3-tetramethyldisiloxane, dimethylpolysiloxane Silicone, dimethylaminomethylpropylsiloxane, polyether modified polysiloxane, polydimethylsiloxane, hexamethylcyclotrisiloxane, hexaethyldisiloxane, Propynyloxytrimethylsilane or hexamethyldisiloxane. The leveling agent can be used alone or in combination of multiple types. The additive (G) may be used alone or in combination of multiple types.

Based on 100 parts by weight of epoxy resin (A), the amount of additive (G) is 0.1 to 3 parts by weight, preferably 0.3 to 2.7 parts by weight, more preferably 0.5 to 2.5 parts by weight Parts by weight. > Preparation method of resin composition >

The preparation method of the resin composition is not particularly limited. For example, the epoxy resin (A), black colorant (B), photoinitiator (C), thermal acid generator (D), polymerizable monomer (E) and solvent (F) are placed under stirring Stir in the vessel to make it uniformly mixed into a solution state, if necessary, additives (G) can also be added, and after mixing them uniformly, a liquid resin composition can be obtained. > Method of manufacturing hardened film >

An exemplary embodiment of the present invention provides a cured film formed using the above-mentioned resin composition.

The cured film can be formed by applying the above-mentioned resin composition on a substrate to form a coating film, and subjecting the coating film to prebake, exposure, development, and postbake. For example, after the resin composition is coated on the substrate to form a coating film, a pre-exposure baking (ie, pre-baking) step is performed at a temperature of 90° C. for 2 minutes. Next, the prebaked coating film was exposed to light of 250 mJ/cm ² . Then, the step of developing the exposed coating film for 60 seconds. Next, post-bake at 220°C for 20 minutes to form a cured film on the substrate.

The substrate may be a glass substrate, a silicon wafer (wafer) substrate, or a plastic base material (for example, a polyether sulfide (PES) board or a polycarbonate (PC) board), and the type thereof is not particularly limited.

The coating method is not particularly limited, but spray coating, roll coating, spin coating or the like can be used, and in general, spin coating is widely used. In addition, a coating film is formed, and then in some cases, residual solvent may be partially removed under reduced pressure. > Method of manufacturing black matrix >

An exemplary embodiment of the present invention provides a black matrix, which is the above-mentioned cured film.

The method of manufacturing the black matrix may be the same as the method of manufacturing the cured film described above, and will not be described here.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples are provided to describe the present invention, and the scope of the present invention includes the categories described in the scope of the following patent applications and their substitutions and modifications, and is not limited to the scope of the examples. Examples of resin composition and cured film

The following describes Examples 1 to 5 and Comparative Examples 1 to 3 of the resin composition and the cured film: Example 1 a. Resin composition

80 parts by weight of epoxy resin (A-1) (purchased from Miwon Specialty Chemical Co., Ltd.), which contains structural units represented by formula (a-1), The structural unit represented by formula (a-2), the structural unit represented by formula (a-4) and the structural unit represented by formula (a-5)), 20 parts by weight of epoxy resin (A-2) (purchased from Dadong) Resin Chemical Co., Ltd., which contains structural units represented by formula (a-1), structural units represented by formula (a-2), structural units represented by formula (a-3), and formula (a-5) ) And the structural unit represented by the formula (a-6)), 241 parts by weight of carbon black, 91 parts by weight of the compound represented by formula (c-2), 91 parts by weight of the compound represented by formula (d-1 ), 151 parts by weight of dipentaerythritol hexaacrylate, 109 parts by weight of bisphenol A diglycidyl ether, 53 parts by weight of glycidyltrimethoxysilane, and 1 part by weight of 3-epoxypropyl After oxypropyl trimethoxysilane was added to 1955 parts by weight of propylene glycol monomethyl ether acetate, and stirred evenly with a stirrer, the resin composition of Example 1 can be obtained. b. Hardened film

The resin compositions prepared in the examples were coated on the substrate by the spin coating method (spin coater model MS-A150, manufactured by Mikasa Co., Ltd., rotating speed 300 rpm). Next, a pre-exposure baking (ie, pre-baking) step was performed at a temperature of 90°C for 2 minutes. Then, light of 250 mJ/cm ² (exposure machine model UX-1000SM, manufactured by Ushio, Inc.) was used for exposure to form a semi-finished product. Next, the step of developing the exposed coating film for 60 seconds. Then, post-bake at 220°C for 20 minutes to obtain a hardened film. The obtained cured film was evaluated by the following evaluation methods, and the results are shown in Table 1. Example 2 to Example 5 and Comparative Example 1 to Comparative Example 3

The resin compositions of Example 2 to Example 5 and Comparative Example 1 to Comparative Example 3 were prepared by the same steps as in Example 1, and the difference lies in: changing the type of resin composition and its usage amount (such as Table 1). The obtained resin composition was made into a cured film and evaluated by the following evaluation methods. The results are shown in Table 1.

[Table 1] Ingredients Example Comparative example 1 2 3 4 5 1 2 3 4 Epoxy resin (A) (parts by weight) Epoxy resin (A-1) 80 50 80 50 80 80 80 80 80 Epoxy resin (A-2) 20 50 20 50 20 20 20 20 20 Black colorant (B) (parts by weight) Carbon black 241 241 241 241 241 241 241 241 160 Photoinitiator (C) (parts by weight) Oxime ester derivatives Compound represented by formula (c-2) 91 91 91 91 91 91 183 91 105 Thermal acid generator (D) (parts by weight) Hexafluoroonium salt Compound represented by formula (d-1) 91 91 91 91 91 91 - - 105 Photo acid generator (parts by weight) Sulfonium salt Compound represented by formula (d-2) - - - - - - - 91 - Polymerizable monomer (E) (parts by weight) Photopolymerizable monomer (E-1) Dipentaerythritol hexaacrylate 151 73 130 109 188 261 151 130 147 Epoxy resin monomer (E-2) Bisphenol A diglycidyl ether 109 188 130 151 73 - 109 130 147 Silane monomer with epoxy group (E-3) Glycidyl trimethoxysilane 53 53 53 53 53 53 53 53 53 Epoxy resin monomer (E-2)/(photopolymerizable monomer (E-1) + epoxy resin monomer (E-2) + siloxane monomer with epoxy group (E-3)) (weight %) 35 60 42 48 twenty three - 35 42 Solvent (F) (parts by weight) Propylene glycol monomethyl ether acetate 1955 1955 1955 1955 1955 1955 1955 1955 2178 Additive (G) (parts by weight) Leveling agent 3-Glyoxypropyloxypropyltrimethoxysilane 1 1 1 1 1 1 1 1 1 Evaluation results Pencil hardness 6H 6H 6H 6H 4H 3H 4H 4H 6H Resolution ◎ ◎ ◎ ◎ ◎ △ ╳ ○ ◎ Reactivity ◎ ○ ◎ ○ ○ △ ◎ △ ◎ Shading ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ △

式（d-2） > 評價方式 > a. 鉛筆硬度 In Table 1, the sulfonium salt is a compound represented by the following formula (d-2).

Formula (d-2) > Evaluation method > a. Pencil hardness

According to ASTM D3363, the pencil hardness of the 1.5 μm hardened film prepared in each example and comparative example was measured. b. Resolution

Use an electron microscope (model: MX-50) with the prepared cured film (with a thickness of 1.5 μm) at a magnification of 500 times to observe whether the line width patterns of different sizes are kept neat and whether the patterns are peeled from the substrate to evaluate the analysis degree.

The evaluation criteria of resolution are as follows: ◎: line width≦10 μm, and not peeling from the substrate; ○: line width≦10 μm, and peeling from the substrate; △: 10 μm<line width≦20 μm, and peeling from the substrate; ╳: 20 μm<line width≦50 μm, and peeled from the substrate. c. Reactivity

In the process of preparing the resin composition into a cured film, the Dektak8 film thickness meter of Veeco Instruments, Inc. was used to measure the film thickness after exposure, development, and post-baking according to the following formula Calculate the residual value:

The evaluation criteria of reactivity are as follows: ◎: 90%≦residual value <100%; ○: 80%≦residual value <90%; △: 70%≦residual value <80%; ╳: 70%≦residual value. d. shading

Measure the shading value of the prepared cured film (with a thickness of 1.5 μm) by a transmission densitometer (model: X-rite 341C).

The evaluation criteria for light-shielding properties are as follows: ◎: 2.5<optical density; ○: 2.0<optical density≦2.5; △: 1.5<optical density≦2.0; ╳: 1.0<optical density≦1.5. > Evaluation Results >

It can be seen from Table 1 that the resin composition includes thermal acid generator (D) and epoxy resin monomer (E-2), and based on the total amount of polymerizable monomer (E) used is 100 parts by weight, epoxy resin The cured film formed by Examples 1 to 5 in which the use amount of the body (E-2) is 15 to 70 parts by weight has good hardness (pencil hardness of 4H or more), resolution, and developability. In contrast, the cured film formed in Comparative Example 1 in which the resin composition does not include the epoxy resin monomer (E-2) had poor hardness, resolution, and developability. In addition, the cured film formed in Comparative Examples 2 and 3 in which the resin composition does not include the thermal acid generator (D) had poor resolution or developability.

In addition, the resin composition includes a cured film prepared by the thermal acid generator (D) (Example 3). The width of the line width pattern of the cured film (Example 3) is 10 μm or less and is not peeled from the substrate, the residual value is less than 10%, and the pencil hardness is 6H . In contrast, the line width pattern of the cured film (Comparative Example 3) prepared from the resin composition in which the thermal acid generator (D) is replaced by the photoacid generator is peeled from the substrate, and the residual value is between 20% and 30% And the pencil hardness is 4H. It can be seen that the cured film prepared by the resin composition including the thermal acid generator (D) has good hardness, resolution and developability, and the resin composition of the thermal acid generator (D) is replaced by the photoacid generator. The hardness, resolution and developability of the prepared cured film are poor.

In addition, the resin composition includes a thermal acid generator (D) and the usage amount based on the epoxy resin (A) is 100 parts by weight, and the usage amount of the photoinitiator (C) is 80 parts by weight to 100 parts by weight. The width of the line width pattern of the cured film (Example 1) is 10 μm or less and is not peeled off from the substrate, the residual value is less than 10%, and the pencil hardness is 6H. In contrast, the width of the line width pattern of the cured film (Comparative Example 2) prepared by excluding the thermal acid generator (D) and the usage amount of the photoinitiator (C) outside the aforementioned range is 20 μm to 50 μm And peeled from the substrate, and the pencil hardness was 4H. It can be seen that the resin composition includes the thermal acid generator (D) and the use amount of the photoinitiator (C) falls within the aforementioned range. The cured film prepared has good hardness, resolution and developability, and does not include thermal The hardness and resolution of a cured film prepared from a resin composition in which the amount of the acid generator (D) and the photoinitiator (C) is not in the aforementioned range is poor. It can be seen that when the amount of epoxy resin (A) is 100 parts by weight and the amount of photoinitiator (C) is 80 to 100 parts by weight, the resin composition can have better patterning ability. , So that the formed cured film has better resolution.

In summary, the resin composition of the present invention contains the thermal acid generator (D) and the epoxy resin monomer (E-2), and based on the total amount of the polymerizable monomer (E) used is 100 parts by weight. When the amount of the oxy resin monomer (E-2) used is 15 parts by weight to 70 parts by weight, the resin composition has good hardness and light-shielding properties, and the cured film formed from it has good light-shielding properties, hardness, and analysis It can be applied to black matrix, and can improve the performance of devices using black matrix.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be determined by the scope of the attached patent application.

no.

no.

no.

Claims (14)

A resin composition including: Epoxy resin (A); Black colorant (B); Photoinitiator (C); The thermal acid generator (D), the thermal acid generator (D) includes a hexafluoroonium salt; Polymerizable monomer (E); and Solvent (F), Wherein the polymerizable monomer (E) includes photopolymerizable monomer (E-1), epoxy resin monomer (E-2) or a combination thereof, based on the total amount of the polymerizable monomer (E) used It is 100 parts by weight, and the usage amount of the epoxy resin monomer (E-2) is 15 to 70 parts by weight. The resin composition according to the first item of the patent application, wherein the structural unit contained in the epoxy resin (A) includes an epoxy-containing structural unit, and the epoxy-containing structural unit has a double key. The resin composition according to item 2 of the scope of patent application, wherein the epoxy group-containing structural unit includes a structural unit represented by the following formula (a-1):

Formula (a-1), * represents the bonding position. The resin composition according to the second item of the patent application, wherein the structural unit contained in the epoxy resin (A) further includes a structural unit having an ethylenically unsaturated group and a structural unit having an aryl group. The resin composition according to item 4 of the scope of patent application, wherein the structural unit having an ethylenically unsaturated group includes at least one of the structural units represented by the following formula (a-2) and formula (a-3) By:

Formula (a-2),

Formula (a-3), * represents the bonding position. The resin composition according to item 4 of the patent application, wherein the structural unit having an aryl group includes the structural unit represented by the following formula (a-4), formula (a-5) and formula (a-6) At least one of:

Formula (a-4),

Formula (a-5),

Formula (a-6), * represents the bonding position. The resin composition according to the first item of the patent application, wherein the photoinitiator (C) includes at least one selected from the group consisting of oxime ester derivatives, halogenated hydrocarbon derivatives and hydrocarbyl acetophenone . The resin composition described in claim 1, wherein the photopolymerizable monomer (E-1) has an ethylenically unsaturated group. The resin composition according to the first item of the patent application, wherein the polymerizable monomer (E) further includes a silane monomer (E-3) having an epoxy group. The resin composition according to item 1 of the patent application, wherein the solvent (F) is selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate and dipropylene glycol methyl ether acetate At least one of the group of. The resin composition according to item 1 of the scope of patent application, wherein the amount of the epoxy resin (A) is 100 parts by weight, and the amount of the thermal acid generator (D) is 20 to 140 parts by weight. Parts by weight. The resin composition according to item 1 of the scope of patent application, wherein the amount of the epoxy resin (A) is 100 parts by weight, and the amount of the black colorant (B) is 200 to 300 parts by weight Parts, the usage amount of the photoinitiator (C) is 20 parts by weight to 140 parts by weight, the usage amount of the polymerizable monomer (E) is 200 parts by weight to 400 parts by weight, and the solvent (F ) The usage amount is 1500 parts by weight to 2500 parts by weight. A cured film is formed of the resin composition described in any one of items 1 to 12 of the scope of patent application. A black matrix, which is a hardened film as described in item 13 of the scope of patent application.