KR20160080523A - Photopolymerizable resin composition, Resin black matrix, and Touch panel - Google Patents

Abstract

The present invention relates to a photopolymerizable resin composition, a resin black matrix, and a touch panel. More specifically, the present invention relates to a photopolymerizable resin composition comprising, based on 100 parts by weight of a binder resin, 40 to 80 parts by weight of a pigment ingredient and 20 to 50 parts by weight of a photopolymerization initiator, and to a resin black matrix for a touch panel using the same. The photopolymerizable resin composition according to the present invention uses a carbon black having high insulation as a pigment, and can obtain a resin black matrix with excellent insulation wherein a surface resistance is 10^14 Ω/□ or higher even after a high temperature post-process at a temperature of 260 degrees by optimizing the contents of a dispersant and a dispersed binder, and a relative dielectric constant value is 50 or lower at 1 MHz.

Description

[0001] The present invention relates to a photosensitive resin composition, a resin black matrix, and a touch panel,

The present invention relates to a photosensitive resin composition and a resin black matrix and a touch panel using the same.

Since a liquid crystal display (LCD) device can not emit light by itself, a separate light source is provided on the rear surface of the device, and the contrast of light is adjusted by controlling the intensity of the transmitted light through liquid crystal provided in each pixel . More specifically, the liquid crystal display device is a device for adjusting the transmittance of light using the electrical characteristics of a liquid crystal material, and is a device that emits light from a light source lamp on the back side of the device, passes through various functional prism films or sheets, The display device is an indirect light emitting type display device in which colors are implemented by passing light through a color filter and images are implemented by controlling the contrast of each pixel by an electrical method.

The color filter typically has a black matrix formed on the upper surface of a substrate made of plastic or glass and has a color such as red (R), green (G), blue (B) Pattern.

Typical methods for producing such a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. In particular, a photopolymerizable composition containing a coloring material is coated on a transparent substrate and exposed to a pattern to be formed, The pigment dispersion method which repeats a series of steps of removing a solvent by using a solvent and repeating a series of steps of heat curing is widely adopted because of high precision of position and thickness of a color filter pixel and durability such as light resistance and heat resistance and few defects such as pinholes have.

Here, the black matrix is indispensable for preventing color mixing between pixels of three colors of red (R), green (G) and blue (B) for high image quality and high contrast display of a liquid crystal display, In the case of an active matrix driving type TFT-LCD using a transistor, a high light shielding property is required.

As a conventional method of manufacturing a black matrix, a method of forming a metal film of chrome or the like on a substrate by vacuum evaporation or the like, coating a photosensitive resin, patterning by photolithography, and etching chrome has been used . The chromium-based black matrix can be formed into a thin film, and has an advantage of obtaining chemical resistance and high light shielding performance. However, since the light reflectance is high, not only the display quality is degraded, but also a separate processing step for total reflection is required. There is a problem that the manufacturing cost is increased due to a vacuum deposition process such as chromium sputtering and chrome etching is required and the waste liquid generated after the etching process causes environmental pollution.

Recently, studies on black matrix using resin have been actively carried out. The resin used for the black matrix produced by the pigment dispersion method is mainly a binder resin, a polymer compound which acts as a support and reacts with light upon exposure to form a photoresist phase, and a polymer compound which reacts with light upon exposure to form a photoresist phase It is composed of components of synthetic monomer. Other than the above, a photosensitive resin composition comprising a pigment, a polymerization initiator, an epoxy resin, a solvent and other additives is prepared.

However, the conventional photosensitive resin composition for black matrix still needs to be further improved in physical properties such as resolution and optical density. In this connection, the applicant of the present invention filed a patent application for a photosensitive resin composition for resin black matrix Literature 0001).

On the other hand, the Inselel touch panel, which is the most popular smart phone structure, is equipped with a sensor capable of performing a touch function in the display panel, which is advantageous for lightness and slimness. By incorporating a touch sensor inside the panel, the weight and thickness of the smartphone can be minimized.

However, since this Inselel touch technology requires the deposition of a touch sensor process integrated in the TFT process, which is a separate process, it is difficult to obtain a high yield and a technical difficulty.

In addition, when a resin black matrix having a high conductivity is applied, there is a problem that an external static electricity flows into the device, which interferes with an electric signal, thereby affecting liquid crystal driving.

In order to obtain a black matrix having high insulating properties, carbon black, titanium black or organic pigment mixed with a surface-treated light shielding material is used. However, the problem that the resistance is lowered when the resin black matrix is heat- have.

Korean Patent Application Publication No. 10-2012-0002372 (published on Jan. 05, 2012)

Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a photosensitive resin composition for a resin black matrix for an LCD color filter to be applied to an in-cell touch panel structure.

The present invention also provides a resin black matrix and a touch panel using the photosensitive resin composition.

In order to accomplish the above object, the present invention provides a photosensitive resin composition comprising 40 to 80 parts by weight of a pigment component and 20 to 50 parts by weight of a photopolymerization initiator based on 100 parts by weight of a binder resin.

According to one embodiment of the present invention, the binder resin is an alkali-soluble acrylic binder resin or a caustic binder resin.

According to another embodiment of the present invention, the alkali-soluble acrylic binder resin is a copolymer obtained by copolymerizing a monomer (A) containing an acid functional group and a monomer (B) copolymerizable with the monomer containing the acid group Chain is a technical feature.

According to another embodiment of the present invention, the monomer (A) comprising the acid group is selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, -Norbornene-2-carboxylic acid, and the monomer (B) is a monomer containing a fluorine group or an epoxy group.

According to another embodiment of the present invention, the pigment component is at least one selected from the group consisting of carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria.

According to another embodiment of the present invention, the carbon black has an average primary particle diameter of 20 to 30 nm, a BET specific surface area of 20 to 110 m 2 / g and a pH of less than 7.

According to another embodiment of the present invention, the photopolymerization initiator is at least one selected from the group consisting of an oxime ester compound, a ketone compound, a halogen compound, a peroxide, and an acylphosphine oxide compound.

According to another embodiment of the present invention, the photosensitive resin composition according to the present invention further comprises at least one member selected from the group consisting of a crosslinking agent, a surfactant, and an adhesion promoter.

Another aspect of the present invention relates to a resin black matrix obtained by applying the photosensitive resin composition onto a substrate and patterning the same, and a touch panel including the resin black matrix.

Another aspect of the present invention relates to a method for forming a resin black matrix, which comprises a step of applying the photosensitive resin composition on a substrate to form a pattern.

The photosensitive resin composition according to the present invention uses carbon black having high insulating property as a pigment and optimizes the content of the dispersant and the dispersed binder so that the surface resistance value is 10 ¹⁴ Ω / Or less, which is excellent in insulating properties, can be obtained.

The present invention will be described in more detail as follows.

BACKGROUND ART [0002] Binder resins are widely used for photosensitive resin compositions in recent years and include a polymer compound that forms a photoresist phase by reaction with light upon exposure to light and a photopolymerizable monomer component that reacts with light upon exposure to form a photoresist image .

Representative examples of the binder resin include a cadmium-based binder resin, an acrylic-based binder resin, a PI (polyimide) -based binder resin, and a novolak-based binder resin.

Cathode binder resin is a resin which can easily control the pattern development through acid value control. It is excellent in heat resistance and electrical characteristics due to pigment affinity, high sensitivity, and structural characteristics, but has a disadvantage in that it has limited molecular weight control.

The acrylic binder can control the molecular weight by the polymerization method, and it is easy to control the pattern flowability, and it is possible to synthesize a binder suitable for the application by introducing various monomers.

PI-based binder resin is an excellent material with high heat resistance. It is an important material for aircraft and computer parts, though it is expensive. It is also excellent in mechanical strength, electrical properties, chemical resistance and radiation resistance. It is used in various forms.

The novolac-based binder resin is a primary resin produced by an acidic catalyst during the production process of a phenolic resin, and is a high-planar high-hardness resin having a high hardness. When an alkaline substance is added thereto, the novolak-

The present invention provides a photosensitive resin composition using the binder resin, and more particularly, it can provide a photosensitive resin composition comprising at least one selected from a cationic binder resin and an alkali-soluble acrylic binder resin.

As the alkali-soluble acrylic binder resin in the binder resin contained in the photosensitive resin composition, a copolymer formed by copolymerization of a monomer (A) containing an acid functional group and a monomer copolymerizable with the monomer (B) Can be used.

In the case of such copolymerization, the strength of the film can be made higher than that of the resin produced by homopolymerization. Or a polymer compound produced by a polymer reaction of the formed copolymer and an ethylenically unsaturated compound containing an epoxy group may be used.

As the alkali-soluble acrylic binder resin, a copolymer formed by copolymerization of a monomer containing an acid group with a monomer copolymerizable with the monomer and an ethylenically unsaturated compound containing an epoxy group are formed by bonding to the copolymer structure The polymer compound may be used together.

Non-limiting examples of the monomer including the acid group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, Carboxylic acids and the like. These may be used alone or in combination of two or more.

In particular, in consideration of the property of the cured film resistant to alkali resistance, it may be preferable to use a binder resin containing an epoxy group. From this point, it may be preferable to use an epoxy group-containing monomer in addition to the monomer containing an acid group in the production of an alkali- .

Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like, but not limited thereto.

The alkali-soluble acrylic binder resin contains a fluorine group from the viewpoint of exhibiting hydrophobicity when forming the resin black matrix by the photosensitive resin composition of the present invention. In consideration of this point, the fluorine group-containing Monomers can be used in combination.

The fluorine group-containing monomer which can be used herein is not particularly limited as long as it is copolymerizable with other monomers and has one carbon double bond. Examples thereof include CH ₂ ═CHC (O) OCHCH ₂ (CF ₂ ) _x CF ₃ (wherein x is an integer of 1 to 12).

The content of the fluorine group-containing monomer may be controlled according to the content of the fluorine group of the monomer, and the fluorine content of the alkali-soluble acrylic binder may be 5 to 50% by weight in view of not inhibiting developability, coating property and dispersion stability It may be desirable to regulate it to be.

The content of the alkali-soluble acrylic binder resin containing the fluorine group may be increased to 5 to 50% by weight based on the total solid content of the photosensitive resin composition, have.

The cadmium-based binder resin refers to an acrylate-based binder resin containing a fluorine group in the main chain, and is not particularly limited in structure.

Examples of the cationic binder resin include compounds represented by the following formula (1).

≪ Formula 1 >

(Wherein X is a compound represented by the following general formula (2)

Y is selected from maleic anhydride, succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 3,4,5 , 6-tetrahydrophthalic anhydride, phthalic anhydride, itaconic anhydride, 1,2,4-benzenetricarboxylic anhydride (1,2, 4-Benzenetricarboxylic Anhydride, Methyl-Tetrahydrophthalic Anhydride, Citraconic Anhydride, 2,3-Dimethylmaleic Anhydride, 1-Cyclopentene-1 2-dicarboxylic anhydride, cis-5-norbornene-2,3-dicarboxylic anhydride, and the like. Anhydride, and 1,8-naphthalic anhydride, wherein the residue of the acid anhydride is selected from the group consisting of

Z is selected from the group consisting of 1,2,4,5-benzene tetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-benzophenonetetracarboxylic dianhydride, pyromelitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, Water (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetracarboxylic anhydride (1,2,4,5-Tetracarboxylic Anhydride), methylnorbornene-2,3-dicarboxylic acid anhydride Methylnorbonene-2,3-dicarboxylic anhydride, 4,4 '- [2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] diphthalic anhydride (4,4' - [2,2 , 2-Trifluoro-1- (Trifluoromethyl) Ethylidene] Diphthalic Anhydride, 4,4'-Oxydiphthalic Anhydride and Ethylene Glycol Bis (Anhydro Trimellitate) Anhydro Trimelitate), Fluorene Diphthalic Anh ydride), < / RTI >

R is hydrogen or an alkyl group having 1 to 12 carbon atoms,

and n is an integer of 1 to 50.)

(2)

(In the formula (2), R is hydrogen or an alkyl group having 1 to 12 carbon atoms.)

A specific example of the process for producing the cationic binder resin includes a compound obtained from the following reaction formula (1).

Scheme 1

The cadmium binder resin is preferably 1 to 40% by weight, more preferably 20 to 30% by weight based on the total solid content of the photosensitive resin composition. If a cocatalyst binder resin containing a fluorine group is used, it may preferably be used in an amount of 5 to 10% by weight based on the total solid content of the photosensitive resin composition, considering hydrophobicity, developability, coating property and dispersion stability .

When 1 to 10 parts by weight of the cationic binder resin (dispersed binder) is added to 100 parts by weight of the binder resin at the time of pigment dispersion, a highly dispersed pigment dispersion can be obtained.

Examples of the dispersion binder include a carotene binder resin, an acrylic binder resin, a PI (polyimide) binder resin, a novolak binder resin, and the like. In the present invention, a pattern of 4 μm or less is realized by applying an alkali-soluble cationic binder resin to a pigment dispersion.

In the present invention, the pigment component is preferably at least one selected from the group consisting of carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria, And the pigment component is included in an amount of 40 to 80 parts by weight based on 100 parts by weight of the binder resin. When the content of the pigment component is less than 40 parts by weight, the optical density is lowered. When the content of the pigment component exceeds 80 parts by weight, pattern stability is deteriorated.

In order to obtain a higher light shielding property, it is necessary to finely disperse the carbon black. In the present invention, carbon black having a pH of less than 7 is used. The pH value of the carbon black is more preferably 4 or less, still more preferably 3 or less. When the pH value of the carbon black is higher than 7, the light transmittance of the black matrix is lowered, and the dimensional accuracy is deteriorated, and film peeling may occur, which is not preferable. The pH value of carbon black is a value obtained by mixing 10 g of carbon black and 100 g of pure water sufficiently by ultrasonication and boiling for 10 minutes so that water does not evaporate. After cooling to room temperature, the pH value of the supernatant is measured with a pH meter, Ion density meter or the like.

In order to make the pH value of the carbon black less than 7, there is a method of oxidizing the carbon powder by contacting with free oxygen at a high temperature after producing the carbon powder, a method of oxidizing by oxidizing agents such as ozone and NO ₂ , And a method of oxidizing it with an oxidizing solution such as acetic acid or sulfuric acid. The pH of the carbon black can be controlled by adding an acidic group such as a carboxyl group or a hydroxyl group to the powder surface of the carbon black.

In order to improve the light shielding property of the black matrix, it is preferable to use carbon black having a small particle diameter. The average primary particle diameter is preferably 5 to 40 nm, more preferably 10 to 35 nm, still more preferably 20 To 30 nm.

When the particle size is less than 20 nm, the surface area of the carbon black particles is too large, so that the cohesive force between the particles is increased to make it difficult to obtain sufficient dispersibility and the stability after dispersion is lowered. The shape and the resolution of the pattern are lowered as wrinkles are generated in the pattern.

The carbon black preferably has a specific surface area of 20 to 110 m 2 / g, more preferably 60 to 70 m 2 / g, as measured by nitrogen adsorption according to the BET method.

If the BET specific surface area of carbon black exceeds 110 m 2 / g, the adsorption amount of the dispersion resin increases to deteriorate the light shielding property of the black matrix, and the viscosity of the carbon black dispersion or photosensitive resin composition becomes high and the dimensional accuracy becomes poor.

Also, the carbon black having the preferable particle diameter of 20 to 30 nm has a BET hardly lower than 20.

In the present invention, the photopolymerization initiator may be at least one selected from the group consisting of an oxime ester compound, a ketone compound, a halogen compound, a peroxide, and an acylphosphine oxide compound. By weight based on 100 parts by weight of the resin. When the amount of the photopolymerization initiator is less than 20 parts by weight, there is a problem in forming a black matrix pattern and in forming a stable pattern profile. When the amount exceeds 50 parts by weight, the line width of the pattern excessively increases.

Examples of the photopolymerization initiator include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) 1 - [(4-phenylthio) phenyl] -1H-pyrazolo [3,4-d] pyrimidin- Phenyl-2-benzoyl-oxime), a compound selected from thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4- Sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacetoxybenzophenone, 2,2'-dimethoxy- methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl- ) - butane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- Ketones such as 1-hydroxycyclohexyl phenyl ketone; Quinones such as anthraquinone and 1,4-naphthoquinone; Tri (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2- chlorophenyl) Halogen compounds such as phenoxy) -s-triazine, phenacyl chloride, tribromomethylphenylsulfone, and tris (trichloromethyl) -s-triazine; Peroxide such as di-t-butyl peroxide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and other acylphosphine oxides.

In the photosensitive resin composition of the present invention, it is preferable to add a dispersant to uniformly and stably disperse the pigment component in the resin solution. Examples of the dispersing agent include a polyester type polymeric dispersant, an acrylic type polymeric dispersant, a polyurethane type polymeric dispersant, a polyarylamine type polymeric dispersant, a pigment derivative, a cationic surfactant, a nonionic surface active agent, an anionic surface active agent and a carboxyimide- .

These dispersants may be appropriately selected depending on the type of pigment. These dispersants may be used alone or in combination of two or more. These dispersants do not have photosensitivity, and therefore, when added in a large amount, there is a risk of deteriorating the photosensitive performance of a target color resist, and it is preferable that the added amount is appropriately determined in consideration of dispersion stability, photosensitive performance and insulation property. But it is not limited thereto.

The photosensitive resin composition according to the present invention may contain a crosslinking agent, and the crosslinking agent may be a multifunctional monomer.

In the present invention, the polyfunctional monomer has a role of forming a photoresist phase by light, and specifically includes propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl 1,6-hexanediol diacrylate, 1,6-hexanediol acrylate, tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxy ethylisocyanurate trimethacrylate Or a mixture of two or more members selected from the group consisting of trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol hexamethacrylate. Lt; / RTI >

In addition, a surfactant may be added to the photosensitive resin composition according to the present invention for the purpose of improving coatability, smoothness of a colored coating film and preventing van der Waals. The addition amount of the surfactant is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, based on the pigment component. If the addition amount is too small, there is no effect of preventing the coating property, the smoothness of the colored coating film and the van der Eckel, and if it is too much, the physical properties of the coating film may be deteriorated.

Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, laurylcarboxymethyl Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate; and silicone surfactants such as polydimethylsiloxane and the like as the main skeleton A surfactant, a fluorine-based surfactant, and the like may be used, but the present invention is not limited thereto.

The photosensitive resin composition according to the present invention may contain an adhesion promoting agent to improve adhesion, and a silane coupling agent may be used as the adhesion promoting agent.

Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, and the like, but the present invention is not limited thereto.

The photosensitive resin composition according to the present invention may contain a solvent. Examples of the solvent include propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate , Ethyl cellosolve acetate, diethyl glycol methyl acetate, ethyl ethoxypropionate, methyl ethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethyl formamide, N, N-dimethylacetamide, N-methylpyrrolidinone, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve. The content of the solvent may be usually about 20 to 90% by weight in the photosensitive resin composition.

The photosensitive resin composition according to the present invention can be produced by a method in which a pigment is dispersed directly in a resin solution using a dispersing machine or a method in which a pigment dispersion is prepared by dispersing a pigment in water or an organic solvent using a dispersing machine, Lt; / RTI >

There are no particular restrictions on the dispersing method of the pigment, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill can be used, but a bead mill is preferable for dispersing effect and fine dispersion. As the beads mill, cobol wheat, basket mill, pin mill, dynomill, and the like can be used.

The resin black matrix using the photosensitive resin composition of the present invention is formed by the following method.

The photosensitive resin composition of the present invention is coated on a substrate and dried to form a film. As the substrate, a transparent substrate such as soda glass, non-alkali glass, quartz glass, or the like is usually used, but the present invention is not limited thereto.

Subsequently, a mask is placed on the film, and ultraviolet rays are irradiated using an exposure apparatus. Subsequently, development is carried out with an alkaline developer. The development method includes, but is not limited to, dipping, spraying, and puddle.

Thereafter, the patterned resin black matrix is obtained by heat treatment (post baking). The heat treatment is usually carried out continuously or stepwise at a temperature of 150 to 300 DEG C, preferably 180 to 250 DEG C for 0.25 to 5 hours in air, in a nitrogen atmosphere or in vacuum.

Thus, the resin black matrix obtained from the photosensitive resin composition of the present invention has an optical density (OD value) of 3.6 or more per unit thickness of 1.0 mu m, a 4 mu m pattern is realized, and a surface resistance value after 260 DEG 3 hours post- 10 ¹⁴ Ω / □ and the permittivity value is less than 50 at 1 MHz.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

< Manufacturing example  1>

232 g of bisphenol fluorene type epoxy compound and 72 g of acrylic acid were mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in a 1 L four-necked flask, and 4.56 g of triethylamine and 100 mg of hydroquinone were added and dissolved by heating at 100 占 폚. The solution was slowly heated in a cloudy state and completely dissolved at 100 ° C.

When completely dissolved, the temperature was maintained at 90 ° C, and nitrogen was injected at a rate of 25 ml / min, which required 12 hours until the acid value reached the target. The acid value was measured, and heating and stirring were continued until it was less than 3.0 mg KOH / g. The mixture was cooled to room temperature to obtain a colorless transparent bisphenol fluorene-type epoxy acrylate.

32.57 g of 1,2,3,6-tetrahydrophthalic anhydride was added to 300 g of bisphenol fluorene epoxy acrylate thus obtained, and the mixture was gradually heated to react at 100 占 폚 for 20 hours to obtain a cationic binder resin represented by the following formula .

(3)

(Wherein n is 5, X is a compound represented by the following formula (4), Y is a compound represented by the following formula (5), and Z is a compound represented by the following formula (6).

&Lt; Formula 4 >

&Lt; Formula 5 >

(6)

< Production Example 2  To 8>

Into a 500-ml plastic block, the composition components and dispersion beads as shown in Table 1 below were added and dispersed with a paint shaker for 8 hours.

Next, the dispersion beads were filtered with a filter screen to prepare a pigment dispersion. In Table 1, the unit is g.

division Carbon black Polymer Dispersant pharmacy
Solseperse12000 Dispersion binder
(Production Example 1) menstruum
(PGMEA) Production Example 2 20 3.5 0.8 2 73.7 Production Example 3 20 3.5 0.8 2 73.7 Production Example 4 20 3.5 0.8 2 73.7 Production Example 5 20 3.5 0.8 2 73.7 Production Example 6 20 3.5 0.8 2 73.7 Production Example 7 20 3.5 0.8 2 73.7 Production Example 8 20 3.5 0.8 2 73.7

Solseperse12000: AVECIA Corporation

   PGMEA: Propylene glycol methyl ether acetate

The physical properties of the carbon black and the polymer dispersant used in the pigment dispersions prepared according to Production Examples 2 to 8 are shown in Table 2 below.

Carbon black Polymer Dispersant A single entry
(Nm) BET
(m ² / g) pH Characteristic Molecular Weight Amine
(MgKOH / g) Acid value Production Example 2 24 65 2.5 PolyUrethane system 25000 47 0 Production Example 3 24 65 2.5 PolyUrethane system 30000 35 0 Production Example 4 24 68 3.1 PolyUrethane system 25000 47 0 Production Example 5 24 101 2.5 PolyUrethane system 25000 47 0 Production Example 6 24 101 2.5 PolyUrethane system 30000 35 0 Production Example 7 24 63 9.3 PolyUrethane system 25000 47 0 Production Example 8 31 64 2.5 PolyUrethane system 25000 47 0

< Example  1 to 3 and Comparative Example  1 to 4>

The alkali-soluble cationic binder resin prepared in Preparation Example 1 and the pigment dispersion prepared in Production Examples 2 to 8 were placed in a flask, and a polyfunctional monomer (dipentaerythritol hexaacrylate) and a photopolymerization initiator were added thereto, Propylene glycol methyl ether acetate (PGMEA)) and other additives (a fluorine-based surfactant, a coupling agent, and an adhesion promoter) were added and stirred for 3 hours to prepare a photosensitive resin composition.

Here, the parts by weight are expressed in parts by weight based on 100 parts by weight of the solid content of the binder resin (Production Example 1).

division Cadmium Binder Resin Pigment dispersion
Photopolymerization initiator menstruum
(PGMEA) Multifunctional monomers
(DPHA) additive
(GPTMS) Example 1


100
Production Example 2


320



34



484



37.5



4.4
Example 2 Production Example 3 Example 3 Production Example 4 Comparative Example 1 Production Example 5 Comparative Example 2 Production Example 6 Comparative Example 3 Production Example 7 Comparative Example 4 Production Example 8

DPHA: dipentaerythritol hexaacrylate

   PGMEA: Propylene glycol methyl ether acetate

GPTMS: glycidoxypropyltrimethoxysilane (Shinetsu)

The development start time, development pattern stability, optical density, residue, surface resistance and dielectric constant of the photosensitive resin compositions prepared in Comparative Examples 1 to 4 and Examples 1 to 3 were measured by the following methods, Are shown in Table 4 below.

(1) Formation of resin black matrix

Using the thus-obtained photosensitive resin composition, a resin black matrix was formed by the following method.

A glass substrate having a clean surface was coated with a spin coater at 400 rpm to form a resin coating layer. After the application, the coated film was dried at 100 DEG C for 100 seconds on a hot plate to give a coating film thickness of 1.5 mu m. Subsequently, an active ray energy line such as ultraviolet ray was exposed through a mask (gap 10 mu m) to an irradiation energy dose of 60 mJ. The exposed film was developed using a developing solution (0.04% KOH aqueous solution, 25 캜) to form a pattern of the resin black matrix. After development, post-baking was performed for 30 minutes after putting in a 230 ° C convection oven. Post-baking was further performed at 260 캜 for 3 hours to measure the surface resistance after the high temperature process.

(2) Development start time

The initiation time of the development was visually confirmed when the resin composition was developed in the development process after the resin composition was coated on the glass substrate-prebake-exposure process and the pattern was started to be formed.

(3) Development pattern stability

The development pattern stability can be evaluated by a method in which a resin composition is coated on a glass substrate, a prebake-exposure process is performed, and then the resin composition is developed in the development process to develop the pattern (formation start time) The line width of the pattern and the straightness of the pattern were confirmed. A period in which the line width of the pattern is reduced to 1 m or less with the developing time of 5 s is confirmed.

(4) Optical density

The optical density of the resin black matrix thus obtained was measured using PMT equipment of Otsuka Electronics Co., Ltd. using a reference having an optical density of 2.4.

(5) Residue

SEM was used to confirm the presence of residues after development.

(6) Surface resistance

The surface resistance of the resin black matrix was measured at 10 V using an MCP-T600 instrument manufactured by Mitsubishi Chemical Corporation.

(7) Permittivity

An aluminum electrode having a thickness of 0.6 mm was formed to a thickness of 2000 Å using a vacuum evaporator (Model: Auto 306, Edward) using the resin black matrix obtained as described above. Capacitance, dielectric loss and relative dielectric constant were measured by selecting three random electrodes at room temperature using an Impedance Analyzer (Model: 4294A, HP).

division
Begin
Time (sec) Development pattern
Stability (sec) Optical density Residue
resolution Surface resistance (Ω / □) permittivity
(1Mhz) 230 占 폚 占 30 min 260 ° C x 3hr 260 ° C x 3hr Example 1 40 15 (good) 3.66 none 4 탆 8.1 x 10 ¹⁴ 5.5 x 10 ¹⁴ 41 Example 2 40 15 (good) 3.67 none 4 탆 4.5 x 10 ¹⁴ 6.3 x 10 ¹⁴ 51 Example 3 42 15 (good) 3.64 none 4 탆 6.9 x 10 ¹⁴ 2.4 x 10 ¹⁴ 56 Comparative Example 1 41 15 (good) 3.69 none 4 탆 6.7 x 10 ¹⁴ 7.4 x 10 ¹² 105 Comparative Example 2 40 15 (good) 3.68 none 4 탆 3.8 x 10 ¹⁴ 7.5 x 10 ¹² 100 Comparative Example 3 42 15 (good) 3.55 none 6 탆 2.0 x 10 ¹⁴ 8.9 x 10 ¹¹ 150 Comparative Example 4 41 15 (good) 3.56 none 6 탆 2.0 x 10 ¹⁴ 7.8 x 10 ¹⁰ 200

From the results of Table 4, it can be seen from the results of the experiment of Comparative Example 3 using Production Example 7 and Comparative Example 4 using Production Example 8 that when the pigment dispersion is produced with carbon black having a high pH value or a large average primary particle diameter, 6 ㎛. It did not satisfy the high resolution property. Also, the surface resistance was decreased and the dielectric constant value was high.

In Examples 1 to 3 using carbon black having a BET specific surface area of 60 to 70 m 2 / g, the dielectric constant was remarkably improved as compared with Comparative Examples 1 and 2 using a carbon black having a BET specific surface area of 101 m 2 / g.

Claims (13)

40 to 80 parts by weight of a pigment component and 20 to 50 parts by weight of a photopolymerization initiator based on 100 parts by weight of the binder resin. The photosensitive resin composition according to claim 1, wherein the binder resin is an alkali-soluble acrylic binder resin or a cadmium-based binder resin. The alkali-soluble acrylic binder resin according to claim 2, wherein the alkali-soluble acrylic binder resin is a copolymer formed by copolymerization of a monomer (A) containing an acid functional group and a monomer (B) copolymerizable with the monomer containing the acid group Wherein the photosensitive resin composition is a photosensitive resin composition. 4. The composition according to claim 3, wherein the monomer (A) comprising the acid group is at least one monomer selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, Nhen-2-carboxylic acid. &Lt; / RTI &gt; The photosensitive resin composition according to claim 3, wherein the monomer (B) is a monomer containing a fluorine group or an epoxy group. The photosensitive resin composition according to claim 1, wherein the pigment component is at least one selected from the group consisting of carbon black, titanium black, acetylene black, aniline black, perylene black, strontium titanate, chromium oxide and ceria. The photosensitive resin composition according to claim 6, wherein the carbon black has an average primary particle diameter of 20 to 30 nm, a BET specific surface area of 20 to 110 m 2 / g and a pH of less than 7. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is at least one selected from the group consisting of an oxime ester compound, a ketone compound, a halogen compound, a peroxide, and an acylphosphine oxide compound. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises at least one selected from the group consisting of a crosslinking agent, a surfactant, and an adhesion promoter. A resin black matrix obtained by applying the photosensitive resin composition of any one of claims 1 to 9 onto a substrate and patterning the resin black matrix. The resin black matrix according to claim 10, wherein the resin black matrix has an optical density (OD) of 3.6 or more per unit thickness of 1.0 mu m, a surface resistance value of 10 ¹⁴ or more, and a dielectric constant at 1 MHz of 50 or less. A touch panel comprising the resin black matrix of claim 11. A process for forming a resin black matrix, which comprises a step of applying the photosensitive resin composition of any one of claims 1 to 9 on a substrate to form a pattern.