TW201510648A - Photo-sensitive resin composition for forming non-display part light-shielding pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a light-shielding pattern on a non-display part and, more specifically, to a photosensitive resin composition for forming a light-shielding pattern on a non-display part which has excellent patternability, visibility, processability and heat resistance by comprising (A) a coloring agent including a pearl pigment, (B) an alkali-soluble binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, wherein the pearl pigment is included at a level of 0.2-2 wt% with respect to the total weight of the composition based on solid contents.

Description

Photosensitive resin composition for forming a non-display portion light-shielding pattern

The present invention relates to a non-display portion light-shielding photosensitive resin composition for forming a non-display portion light-shielding pattern, in particular, a non-display portion light-shielding pattern photosensitive resin composition for good visibility, processability, and heat resistance.

In recent years, with the rapid development of semiconductor technology, the demand for higher performance display devices has rapidly increased due to miniaturization and light weight development.

From the trend of informationization, electronic displays used to visually convey information appear in various forms. Recently, with the development of mobile communication, the demand for the development of portable displays has been quite high.

The display devices are converted from a video tube type to a liquid crystal display (LCD), a plasma display panel (PDP), and an organic light-emitting diode (OLED). In particular, liquid crystal displays (LCDs) have lower power consumption, miniaturization, and lighter weight than conventional image tube displays, and do not release harmful electromagnetic waves. Therefore, as a second-generation display of the next generation, almost all information processing machines are equipped with display devices. In addition, recently, due to the spread of smart phones, the use of such touch devices integrated with touch sensors has been rapidly increasing.

As shown in FIG. 1 , taking a mobile phone as an example, a cover window substrate is disposed on the outermost surface, and an image is displayed on the entire surface of the cover window substrate, and the display portion of the touch input portion and the surrounding portion should be divided as needed. A non-display portion of the display portion of the image sensor.

The display portion light-shielding pattern is formed on the non-display portion, and has a function of hiding the opaque conductive wiring pattern and various circuits, and may also print a trademark or logo of the mobile phone manufacturer as needed. In the prior art, since the non-display portion is mainly used for hiding patterns and circuits, it is a common practice to form a simple hue layer. A technique for forming an edge pattern by a thermosetting black ink composition as disclosed in Korean Laid-Open Patent Publication No. 2013-56598.

On the other hand, recently, considering various preferences of consumers and the beauty of the display, a coating composition having various colors is used, but when a bright color coating composition such as white or pink having low light-shielding property is used as a non-display In the case of the coating material of the portion, the inside of the display is easily exposed. Therefore, a gray or black coating layer is disposed under the coating layer formed of the bright color coating composition to form a non-display portion.

However, in the case where the non-display portion is formed by the coating layer in this manner, although the optical density (Optical Density) is increased due to the gray or black coating layer of the lower layer, the light shielding ratio is improved, but the upper layer is The high light transmittance of the bright coating layer results in the problem that the underlying layer of gray or black coating layer can be visually recognized. Therefore, the industry has studied many methods to improve this problem. In addition, considering the aesthetics of the display, many efforts have been made to reflect the high reflection brightness of the non-display portion described above.

In addition, the demand and supply of display devices driven by touch methods have recently been greatly expanded. According to the driving method, the touch panel has a resistive type, an electrostatic type, a SAW type, an infrared type, etc., but mainly uses an electrostatic type that is driven by static electricity emitted from a human body. In the past, in addition to tempered glass placed on the entire surface of the product, one or two internal glass plates or transparent films were additionally inserted inside the tempered glass to vacuum-deposit the ITO pattern, and then the inner glass plate was transparent or transparent. The ITO pattern is formed on both sides of the film or each of them is assembled to complete the touch panel. However, since the thickness of the touch panel has become thick, in recent years, the ITO pattern is directly vacuum-deposited on the tempered glass to manufacture the touch panel. In the above manner, the non-display portion is formed on the tempered glass, and the ITO pattern is also directly formed. Therefore, the non-display portion formed by the tempered glass is exposed to chemicals in a process such as a lithography for forming an ITO electrode, and is also exposed to a high temperature during heat treatment of the ITO electrode. Therefore, the chemical resistance and heat resistance of the coating material of the non-display portion of the touch panel are required to be particularly important functions.

In particular, after the high-temperature post-treatment step, the yellowing of the plating film in the non-display portion is detrimental to the appearance, and thus the use of the product is restricted. Therefore, research for solving this problem is also considerable. [Prior Art Literature] [Patent Literature]

Korean Public Patent No. 2013-56598

[Problems to be solved by the invention]

An object of the present invention is to provide a non-display portion light-shielding pattern photosensitive resin composition which is excellent in appearance and visibility.

The present invention has an object of providing a photosensitive resin composition for forming a non-display portion light-shielding pattern, which can exhibit good heat resistance even when heat-treated at a high temperature, thereby having high reliability, pattern formability, and good residual film ratio. .

Further, the present invention has an object of providing a photosensitive resin composition for forming a non-display portion light-shielding pattern, having good photosensitivity, and having a good three-dimensional feeling after curing and a texture appearance. [solution to solve the problem]

A photosensitive resin composition for forming a non-display portion light-shielding pattern, comprising: a coloring agent (A) comprising a pearl pigment, an alkali-soluble binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiation The agent (D) and the solvent (E), wherein the aforementioned pearl pigment contains the amount of the composition in an amount of 0.2 to 2% by weight based on the total weight of the composition based on the solid content.

2. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the above item 1, wherein the pearl pigment has an average particle diameter of 5 to 15 μm.

3. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the above item 1, wherein the pearl pigment comprises a reflection layer core portion and a high refractive index layer coated on the core portion.

4. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the above item 3, wherein the core portion of the reflective layer is mica, sericite, talc, kaolin, bentonite clay mineral, plate-like titanium oxide, and plate At least one of the group consisting of cerium oxide, platy alumina, boron nitride, barium sulfate, and platy titanium dioxide/cerium oxide erbium oxide.

5. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the above item 3, wherein the high refractive index layer comprises titanium oxide (TiO ₂ ), zirconium dioxide (ZeO ₂ ), antimony trioxide. Any one selected from the group consisting of (Sb ₂ O ₃ ), zinc sulfide (ZnS), tin dioxide (SnO ₂ ), and zinc oxide (ZnO).

6. A window substrate having a non-display portion, wherein the non-display portion is formed by forming a non-display portion light-shielding pattern photosensitive resin composition as described in any one of items 1 to 5 above.

A touch screen panel comprising the window substrate described in the above item 6.

An image display device comprising the touch screen panel described in the above item 7.

The photosensitive resin composition for forming a non-display portion light-shielding pattern of the present invention exhibits good visibility, three-dimensionality and texture by containing a pearl pigment of a specific content range, and exhibits good heat resistance even when heat-treated at a high temperature. , so it shows good reliability. In addition, it also exhibits good processability and pattern formability.

The present invention relates to a photosensitive resin composition for forming a non-display portion light-shielding pattern, comprising a pearl pigment-containing coloring agent (A), an alkali-soluble binder resin (B), a photopolymerizable compound (C), and photopolymerization. The initiator (D) and the solvent (E), wherein the pearl pigment has a ratio of 0.2 to 2% by weight based on the total weight of the composition based on the solid content, and has a good pattern and visibility. Processability and heat resistance.

The contents of the present invention are explained in more detail below.

Colorant (A) The colorant of the present invention comprises a pearl pigment.

The pearl pigment of the present invention is a pearl luster pigment having multiple hue, and is a collective name for displaying colors such as pearl color, iridescence color, and metallic color. The pearl pigment used in the present invention not only has a good aesthetic feeling, but also has a high reflectance, and the three-dimensional feeling and the specific display performance in texture are excellent. Further, since the irradiated light can be uniformly scattered inside the composition at the time of hardening, a good pattern can be formed.

The pearl pigment used in the present invention may have a core portion of a reflective layer and a high refractive index layer coated on the core portion. The specific material of the core portion of the reflective layer and the high refractive index layer can be variously selected according to the desired hue, reflectance, and the like.

The core of the reflective layer can be made of mica, sericite, talc, kaolin, bentonite clay mineral, platy titanium dioxide, platy cerium oxide, platy alumina, boron nitride, barium sulphate, and platy titanium dioxide. / cerium oxide, a mixed oxide, etc., and these materials may be used singly or in combination of two or more.

The high refractive index layer may comprise titanium dioxide (TiO ₂ ), zirconium dioxide (ZeO ₂ ), antimony trioxide (Sb ₂ O ₃ ), zinc sulfide (ZnS), tin dioxide (SnO ₂ ), oxidation. Zinc (ZnO) or the like may be used alone or in combination of two or more.

The pearl pigment of the commercially available product is, for example, R-900D, R-900F, R-901D, R-901F, etc., manufactured by CQV Co., Ltd., but is not limited thereto.

The refractive index of the high refractive index layer is preferably from 2.4 to 3.0. If in the above numerical range, good reflectance, stereoscopic effect and texture of the pearl pigment can be exhibited.

The pearl pigment used in the present invention preferably has an average particle diameter of 5 to 15 μm. The composition has superior storage stability by using a pearl pigment having an average particle diameter of the aforementioned numerical range.

When the average particle diameter is less than 5 μm, the visibility is lowered. When it exceeds 15 μm, the nozzle is clogged when the composition is applied, or the pattern is not easily formed due to a decrease in the uniformity of the coated surface.

The pearl pigment of the present invention contains the amount of 0.2 to 2% by weight based on the total weight of the composition based on the solid content. When the content is less than 0.2% by weight, the visibility is lowered, and when it exceeds 2% by weight, the processability is lowered.

Regarding the coloring agent of the present invention, in addition to the above pearl pigment, a coloring agent well known in the technical field within the scope of the present invention, such as a dye and a pigment, may be further included.

Alkali-Soluble Binder Resin (B) The alkali-soluble binder resin is a resin which is soluble in the solvent of the present invention, has a function as a binder resin for a colorant, and is soluble in an alkaline developing solution. No special restrictions are required for use.

The binder resin may, for example, be a carboxyl group-containing monomer, a copolymer of the monomer and other monomers copolymerizable therewith, or the like.

The carboxyl group-containing monomer may, for example, be an unsaturated carboxylic acid such as an unsaturated polyvalent carboxylic acid having one or more carboxyl groups in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid. .

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like.

The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polyvalent carboxylic acid may be a mono(2-methylpropenyloxyethylalkyl)ester, and examples thereof include succinic acid mono(2-propenyloxyethyl ester) and succinic acid. Mono(2-methylpropenyloxyethylethyl ester), phthalic acid mono(2-propenyloxyethyl ester), phthalic acid mono(2-methylpropenyloxyethylethyl ester), and the like. The above unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone. Methacrylic acid, etc.

The carboxyl group may contain a single monomer, and may be used singly or in combination of two or more kinds thereof.

Examples of the monomer and the copolymerizable monomer contained in the carboxyl group include styrene, α-methyl methyl styrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, and p-. -chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl Aromatic vinyl compounds such as methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and hydrazine: methyl acrylate, methacrylic acid Ester, ethyl acrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, isopropyl methacrylate, isopropyl acrylate, n-butyl methacrylate, n-butyl acrylate, methacrylic acid Butyl ester, isobutyl acrylate, sec-butyl methacrylate, sec-butyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, ethyl 2-hydroxyacrylate, 2-hydroxy methacrylate ethyl ester, 2 -hydroxy acrylate propyl ester, 2-hydroxy methacrylate propyl ester, 3-hydroxyl Propyl acrylate, 3-hydroxypropyl methacrylate, butyl 2-hydroxyacrylate, butyl 2-hydroxymethacrylate, butyl 3-hydroxyacrylate, butyl 3-hydroxymethacrylate, 4-hydroxyacrylic acid butyl Ester, butyl 4-hydroxymethacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methacrylic acid Phenyl ester, ethyl 2-methoxyacrylate, ethyl 2-methoxyethyl acrylate, ethyl 2-phenoxy acrylate, ethyl 2-phenoxy methacrylate, methoxy diglycol acrylic acid Ester, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylic acid Ester, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-hydroxy-3-benzene An unsaturated carboxylic acid ester such as propyl methacrylate, monoglyceride or glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylamino group Ethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-Dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethyl Aminoalkyl esters of unsaturated carboxylic acids such as propylaminopropyl methacrylate; glycidyl acrylates of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; vinyl phthalate, vinyl propionate, Vinyl vinyl esters such as vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; acrylonitrile, methacrylonitrile, and α a cyanide vinyl compound such as chloroacrylonitrile or vinyl cyanide; acrylamide, decyl methacrylate, α-chlorinated Unsaturated guanamines such as anilide, N-2-hydroxyethyl propylene decylamine, N-2-hydroxyethyl methacrylate decylamine; maleimide, N-phenyl cis-butene Unsaturated quinone imines such as diimine, N-cyclohexylmethyleneimine, etc.; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene, etc. And at the end of the molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polyoxyalkylene polymer A monopropylene fluorenyl group or a macromonomer having a monomethacryl fluorenyl group or the like. The monomers herein may be used singly or in combination of two or more.

When the binder resin is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer, the content ratio of the constituent units derived from the carboxyl group-containing monomer is such that the total constituent unit content is configured as described above. It is 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight. When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is from 10 to 50% by weight based on the above criteria, the solubility in the developing solution is good, and the pattern can be accurately formed during development, which is preferable.

As the binder resin, for example, (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylate / methyl (meth) acrylate / polystyrene macromolecular copolymer, (meth) acrylic acid /(Meth)methyl acrylate/polymethyl(meth)acrylate macromonomer copolymer, (meth)acrylic acid/benzyl (meth) acrylate/polystyrene macromonomer copolymer, (Meth)acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl Base (meth) acrylate / polystyrene macromer copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly methyl (a Acrylate macromonomer copolymer, (meth)acrylic acid/styrene/benzyl (meth) acrylate/N-phenyl maleimide copolymer, (Meth)acrylic acid/succinic acid mono(2-propene oxime)/styrene/benzyl (meth) acrylate/N-phenyl maleimide copolymer, (meth)acrylic acid/amber Acid mono(2-propenyloxyethyl ester) / styrene / allyl (meth) acrylate / N-phenyl maleimide copolymer, (meth) acrylic acid / benzyl (methyl ) acrylate / N-phenyl maleimide / styrene / glycerol mono (meth) acrylate copolymer.

Among these, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate/styrene copolymer, (meth)acrylic acid/( Methyl)methyl acrylate copolymer, (meth)acrylic acid / methyl (meth) acrylate / styrene copolymer is preferred.

The binder resin is not particularly limited, but preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 3,000 to 50,000, or more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin is in the range of 3,000 to 100,000, the colorant is relatively easy to disperse, has low viscosity, and has good storage stability, and therefore is preferable.

The binder resin may be 3 to 80% by weight, and preferably 5 to 70% by weight, based on the total weight of the solid component in the non-display portion light-shielding photosensitive resin composition. When the content of the binder resin is from 3 to 80% by weight based on the above-mentioned standard, the coloring agent is easily dispersed and the storage stability is also good, which is a preferable condition.

Photopolymerizable compound (C) The photopolymerizable compound is a compound which can be polymerized by the action of a photo and photopolymerization initiator, and a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers can be used. .

Specific examples of the monofunctional monomer include mercaptophenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexanol carbitol acrylate, 2-hydroxyethyl Ester acrylate, N-vinyl pyrrolidone, and the like.

Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxy group. Triterpene methyl propane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa Methyl) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Among the photopolymerizable compounds exemplified in the above examples, it is preferred to use a difunctional or higher polyfunctional monomer, and a trifunctional or higher (meth) acrylate, and a urethane (A). The acrylate is particularly preferable because it has good polymerizability and can be improved in strength. The photopolymerizable compounds in the above examples may be used alone or in combination of two or more.

The photopolymerizable compound may have a total weight of the solid component in the non-display portion light-shielding photosensitive resin composition of from 1 to 60% by weight, preferably from 5 to 50% by weight. When the photopolymerizable compound is in the above numerical range, good pixel portion strength and smoothness can be obtained.

Photopolymerization initiator (D) The photopolymerization initiator may be a photopolymerization initiator commonly used in the above-mentioned art, and is not particularly limited. For example, a triazine compound, an acetophenone compound, or a diimidazole system can be used. At least one of the group consisting of the compound and the terpenoid is selected.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-double. (trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)ethene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-furan-2-yl Ethylene]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethene-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethene]-1,3,5-triazine, and the like.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2- Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methyl ester Thiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxyl -2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1 -(4-morpholinophenyl)butan-1-one and the like.

Specific examples of the above diimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis (2, 3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Alkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole, 2,2-double (2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, or substituted with a carbon alkoxy group 4,4',5,5 'Phenyl imidazole compound and the like. Among them, 2,2'-bis(2-chlorophenylchlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis (2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-diimidazole is preferred.

Specific examples of the hydrazine compound include o-ethoxycarbonyl-α-hydroxyimino-1-phenylpropan-1-one. Commercially available products include OXE01 and OXE02 from BASF.

Further, other photopolymerization initiators may be used in combination without detracting from the effects of the present invention. Further, the above photopolymerization initiator may also be used in combination with a photopolymerization initiation aid commonly used in the art.

Specific examples thereof may be an amine compound or a carboxylic acid compound. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoin Acid ethyl ester, 4-dimethylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid-2-ethylhexanol, benzoic acid (2-dimethylamino) ethyl ester, N, N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone (common name: micbeone), 4,4'-di(diethylamino)diphenyl An aromatic amine compound such as a ketone or the like, and preferably the aforementioned amine compound may be an aromatic amine compound.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthio Acetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalene An aromatic isophthalic acid such as thioacetic acid, N-naphthylglycine or naphthyloxyacetic acid.

The photopolymerization initiator accounts for 1 to 40% by weight, preferably 3 to 20% by weight, based on the total weight of the solid component in the non-display portion light-shielding photosensitive resin composition. When the photopolymerization initiator is in the above content range, the exposure time can be shortened by the improvement of the sensitivity, and the productivity is also improved.

Solvent (E) The aforementioned solvent is not particularly limited. Preferably, an ether, an aromatic hydrocarbon, a ketone, an alcohol, an ester or a decylamine can be used.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diglyme, diethylene glycol diethyl ether, and diethylene glycol. Ethers such as dipropyl ether and diethylene glycol dibutyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and trimethylbenzene; methyl ethyl ketone, acetone, methyl amyl ketone, and methyl isobutyl ketone , ketones such as cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; ethyl 3-ethoxypropionate, 3-methoxypropionic acid Ester, methyl cyproterone acetate, ethyl cyproterone acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, butyl 3-methoxyacetate , 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetic acid Ester, propylene glycol monomethyl ether acetate, propylene glycol Ether acetate, diethyl carbonate stretch, propylene carbonate or γ- butyrolactone, etc. esters. Among the solvents exemplified above, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, and 3 are preferable in terms of coatability and dryness. Ethyl ethoxypropionate, methyl 3-methoxypropionate, and the like are used as the solvent exemplified above, and may be used singly or in combination of two or more.

The solvent is preferably 30 to 90% by weight, and preferably 50 to 80% by weight, based on the total weight of the photosensitive resin composition for forming the non-display portion light-shielding pattern.

When the solvent is contained in the above numerical range, the coating property at the time of coating the composition is good, which is preferable.

Additive (F) The photosensitive resin composition for forming a non-display portion light-shielding pattern of the present invention may further contain a filler, other polymer compound, a hardener, a surfactant, a pigment dispersant, and adhesion promotion in accordance with a desired condition. Additives such as agents, antioxidants, UV absorbers, and anticoagulants.

Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like.

Specific examples of the other polymer compound include curable resins such as an epoxy resin and a maleimide resin; polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. A thermoplastic resin such as an ester, a polyester or a polyurethane.

The curing agent is for improving deep hardenability and mechanical strength, and an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, or the like may be used.

Examples of the epoxy compound include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, and a novolac epoxy resin. Other aromatic epoxy resins, cycloaliphatic epoxy resins, epoxypropyl ester resins, epoxypropylamine resins, or bromine derivatives of such epoxy resins, epoxy resins and their bromine derivatives Aliphatic, alicyclic and aromatic epoxy compounds, butadiene (co)polymer epoxy compounds, isoprene (co)polymer epoxy compounds, epoxypropyl (meth)acrylic acid Ester (co)polymer, triepoxypropyl isocyanurate, and the like.

Examples of the oxetane compound include carbonate dioxetane, xylene dioxetane, dioxetane adipate, and dioxetane phthalate. And cyclohexanedicarboxylic acid dioxetane and the like.

The hardening agent may include a hardening auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound or an oxetane skeleton of an oxetane compound together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As the above-mentioned anhydrous carboxylic acid, a commercially available epoxy resin hardener can be used. For example, ADEKA HARDENER EH-700 (made by ADEKA CORPORATION), trade name RIKACID HH (manufactured by Nippon Chemical and Chemical Co., Ltd.), and trade name MH-700 (manufactured by Nippon Chemical and Chemical Co., Ltd.) Etc., the above curing agent may be used singly or in combination of two or more.

The surfactant is preferably a fluorine-based surfactant or a polyoxyn-based surfactant. Commercially available products of the above-mentioned polyoxosiloxane surfactant are, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, and TSF-4445 manufactured by GE Toshiba Silicone Co., Ltd. TSF-446, TSF-4460, TSF-4452, etc. Commercial products of the fluorine-based surfactant include, for example, MEGA FUCK F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals Co., Ltd., and TF-made by DIC Corporation. 1535 and so on.

The above-exemplified surfactants may be used singly or in combination of two or more. These surfactants usually comprise from 0.01 to 10% by weight, preferably from 0.05 to 2% by weight, based on the total weight of the solid components used to form the non-display portion light-shielding photosensitive resin composition.

The pigment dispersant may be an additive for pigment depolymerization and maintaining stability, and the dispersant may preferably further contain BMA (butyl methacrylate) or DMAEMA (N, N-methyl group). Acrylic dispersant of dimethylaminoethyl acrylate). In this case, the acrylic dispersant is preferably produced by the activity control method described in the Korean Patent Publication No. 2004-0014311, and the commercially available acrylic dispersant manufactured by the above-described activity control method is: DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. Further, the aforementioned dispersing agent may also contain a known resin type pigment dispersing agent, in particular: a polycarboxylate represented by polyurethane, polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) An amine salt, a polycarboxylic acid ammonium salt, a polycarboxylic acid alkylamine salt, a polyoxyalkylene oxide, a long-chain polyaminoguanamine phosphate, a hydroxyl group-containing polycarboxylate, and a modified product of the above, or Is a guanamine formed by the reaction of a polyester containing a free carboxyl group with a poly(lower alkylamine) or an oleaginous dispersant of these salts; (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-( Water-soluble resin such as methyl acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone or water-soluble polymer compound; polyester; modified Polyacrylate; an additional product of ethylene oxide/propylene oxide, and a phosphate ester.

As a commercial product of the above-mentioned resin-based pigment dispersant, it is a cationic resin dispersant, and for example, BYK Chemical Company's trade name: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-180, DISPER BYK-182, DISPER BYK-184, trade names of BASF: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800, Lubirzol Product Name: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10, Chuanyan FINE CHEMICAL Company's trade name: (HINOACT) T-6000, (HINOACT) T-7000, (HINOACT) T-8000, taste The product name of the company: (AJISPER) PB-821, (AJISPUR) PB-822, (AJISPUR) PB-823, the name of the company (FLORENE) DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA -33, FLORENE DOPA-44, etc.

The dispersing agent preferably contains the amount of 0.01 to 10% by weight, particularly preferably 0.05 to 2% by weight, based on the total weight of the solid component for forming the non-display portion light-shielding photosensitive resin composition. In the case where the dispersing agent contains the above content, the dispersibility of the pigment as a coloring agent is particularly excellent, which is preferable.

As the adhesion promoter, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-aminoethyl)-3-amino group is exemplified. Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3 -Chloropropyltrimethoxyoxane, 3-methylpropenyloxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxyoxane, 3-isocyanatopropyltrimethoxydecane, 3-isocyanatopropyl Base triethoxy decane and the like.

These adhesion promoters may be used singly or in combination of two or more kinds, and the total weight of the solid component in the non-display portion light-shielding photosensitive resin composition is usually 0.01 to 10% by weight, preferably Contains an amount of 0.05 to 2% by weight.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-tert-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxydiphenyl ketone.

As the anticoagulant, sodium polyacrylate and the like are listed.

The photosensitive resin composition for forming a non-display portion light-shielding pattern of the present invention is applied onto a non-display area on a window substrate to form a light-shielding pattern of the non-display portion. The light blocking pattern can be formed by methods known in the art such as screen printing, photolithography, lithography, and the like.

The window substrate formed by the light-shielding pattern of the present invention can also be used as a window substrate of a touch screen panel, and the touch screen panel can be combined with an image display device such as a liquid crystal display, an OLED or a flexible display. Achieve effective use.

The preferred embodiments are described below to make the present invention easier to understand, but these examples are merely illustrative of the invention and are not intended to limit the scope of the application. Various changes and modifications of the embodiments are possible within the scope of the invention and the scope of the invention, which is obvious to those skilled in the art, and such changes and modifications are of course also claimed.

Embodiment 1 100% of the total weight of the solid content of the composition, average particle size 7μm pearl pigment (R-901F, CQV Co., Ltd.) 0.2% by weight, copolymers of methacrylic acid and methyl methacrylate of benzyl (weight average molecular weight Mw: 15,000) 46.8 wt%, dipentaerythritol hexaacrylate (TOAGOSEI) 46.8 wt%, photopolymerization initiator I-819 (manufactured by BASF Corporation) 5.5% by weight, surfactant TF-1535 ( 0.1% by weight of DIC Corporation, 0.5% by weight of dispersant BYK-180 (manufactured by BYK Co., Ltd.), 0.1% by weight of adhesion promoter 3-isocyanatopropyltriethoxyoxane, and solvent propylene glycol methyl ether acetate. After mixing at a ratio of 50% by weight based on the total weight of the composition, the mixture was stirred for 2 hours to prepare a non-display portion light-shielding pattern photosensitive resin composition.

Embodiment 2 using 1% by weight of the pearl pigment, remaining the same manner as in Embodiment 1 to prepare a composition.

In the third embodiment, 2% by weight of pearl pigment was used, and the composition was prepared in the same manner as in the first embodiment.

In the fourth embodiment , a pearl pigment (R-901D, manufactured by CQV Co., Ltd.) having an average particle diameter of 14 μm was used, and the composition was prepared in the same manner as in the first embodiment.

In the fifth embodiment , a pearl pigment (R-901D, manufactured by CQV Co., Ltd.) of 1% by weight and an average particle diameter of 14 μm was used, and the composition was prepared in the same manner as in the first embodiment.

In the sixth embodiment , a pearl pigment (R-901D, manufactured by CQV Co., Ltd.) of 2% by weight and having an average particle diameter of 14 μm was used, and the composition was prepared in the same manner as in the first embodiment.

In the seventh embodiment , a pearl pigment (R-901D, manufactured by CQV Co., Ltd.) of 1% by weight and an average particle diameter of 17 μm was used, and the composition was prepared in the same manner as in the first embodiment.

Comparative Form 1 0.1% by weight, an average particle diameter of 7μm pearl pigment, remaining in the same manner as Embodiment 1 to prepare a composition.

Comparative Embodiment 2 using 5% by weight, an average particle diameter of 7μm pearl pigment, remaining in the same manner as Embodiment 1 to prepare a composition.

In Comparative Example 3 , a pearl pigment of 0.1% by weight and an average particle diameter of 14 μm was used, and the composition was prepared in the same manner as in Example 1.

In Comparative Example 4 , a pearl pigment of 5% by weight and an average particle diameter of 14 μm was used, and the composition was prepared in the same manner as in Example 1.

Comparative Example 5 A white pigment titanium dioxide having a weight of 300 nm and an average particle diameter of 300 nm was used, and the composition was prepared in the same manner as in the first embodiment.

In Experimental Example 1 , a light-shielding pattern was produced by using the photosensitive resin composition for forming a non-display portion light-shielding pattern prepared in the above-described first to seventh embodiments and comparative examples 1 to 5. That is, the photosensitive resin compositions of the above-described first to seventh embodiments and comparative examples 1 to 5 were applied onto a glass substrate by spin coating, and then maintained at a temperature of 100 ° C for 3 minutes on a hot plate. A film is formed. Next, a photomask having a linear pattern of 3 to 100 μm was placed on the film to irradiate ultraviolet rays. At this time, the ultraviolet light source was irradiated at 100 mJ/cm ² using a 1 kW high pressure mercury lamp including all the g, h, and i lines. The film irradiated with ultraviolet rays was immersed in an aqueous KOH solution having a pH of 10.5 for 100 seconds and developed. The glass plate to which the film was applied was washed with distilled water, dried with nitrogen, and heated in a heating furnace at 230 ° C for 20 minutes to produce a light-shielding pattern layer. The thickness of the light-shielding pattern layer produced here was 15.0 μm.

Experimental Example 2 (1) Preparation Example 1: Preparation of a colorant dispersion composition 35.0 g of a titanium dioxide (CI Pigment White 6) colorant having an average particle size of 200 nm, and 4.94 g of a binder resin (methacrylic acid and benzyl methacrylic acid) a copolymer of ester wherein the ratio of methacrylic acid unit to benzyl methacrylate unit is 31:69 mole ratio, polystyrene equivalent weight average molecular weight is 20,000), dispersant BYK-180 (BYK company) 4.32 g. The solvent propylene glycol methyl ether acetate 55.74 g or the like was mixed and dispersed for two hours in a bead mill to prepare a colorant dispersion composition.

(2) Preparation Example 2 : 50.2 g of a colorant dispersion composition prepared by preparing the light-shielding layer photosensitive resin composition prepared in Preparation Example 1, a copolymer of methacrylic acid and benzyl methacrylate 29.5 g (methyl group) The ratio of the acrylic acid unit to the benzyl methacrylate unit is 31:69 mole ratio, the weight average molecular weight in terms of polystyrene is 20,000), dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 11.1 g, 2-methyl-(4-methylthiophenyl)-2-morpholinyl-1-propan-1-one (Irgacure 907-; manufactured by BASF Corporation) 2.2 g, 2,4-diethylthioxanthone (Speedcure DETX; manufactured by LAMBSON Co., Ltd.), 1.1 g, 3-methylpropenyloxypropyltrimethoxysilane (KBM-503; manufactured by Shin-Etsu Co., Ltd.), 0.4 g, and propylene glycol methyl ether acetate 5.5 g, etc., were mixed and prepared. A photosensitive resin composition for forming a full-surface light-shielding layer of the display device.

(3) Formation of light-shielding pattern The light-shielding layer for forming the entire surface prepared by the above-mentioned Experimental Example 1 for forming a pattern photosensitive resin composition was used. In other words, the photosensitive resin composition for forming a full-surface light-shielding layer prepared by the above-described first to seventh embodiments and comparative examples 1 to 5 is used as a lower film, and the upper portion thereof is coated with a preparation example 2 in accordance with spin coating. After the composition prepared by the method, it was placed on a hot plate and maintained at a temperature of 100 ° C for 3 minutes to form a film. Next, a photomask having a linear pattern of 3 to 100 μm was placed to irradiate ultraviolet rays. At this time, the ultraviolet light source was irradiated at 100 mJ/cm ² using a 1 kW high-pressure mercury lamp including all the g, h, and i lines. The film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 100 seconds, and developed. The substrate coated with this film was washed with distilled water, dried with nitrogen, and heated in a heating furnace at 230 ° C for 20 minutes to form a light-shielding pattern layer. The thickness of the light-shielding pattern produced here was 20.0 μm.

1. Confirmation of patterning property of the light-shielding pattern In the process of producing the light-shielding pattern of Experimental Example 1, the patterning property was confirmed in the following manner while measuring the development speed, and the results are shown in Table 1 below. *: Pattern: based on a regular square pattern of 250 μm length. ◎: The pattern has no notch and has a regular square shape. ○: A part of the pattern is notched, but has a substantially square shape. △: There are many gaps in the interface of the pattern, and there is no square shape. ╳: There are many gaps in the pattern, resulting in a broken shape and the shape of the pattern cannot be confirmed.

2. Confirmation of the visibility of the light-shielding pattern The visibility between the respective patterns of the light-shielding pattern produced in Experimental Example 2 on the glass surface was confirmed, and the results are shown in Table 1 below. *: Identification: Based on a regular square pattern of 250 μm long. ◎: The pattern boundary is conspicuous, and the pattern shape can be confirmed. ○: Although the pattern boundary is not obvious, the pattern shape can be roughly confirmed. △: The pattern boundary was not obvious, and the pattern shape could not be confirmed. ╳: The pattern boundary is broken and the shape of the pattern cannot be confirmed.

3. Evaluation of the heat-resistant coating composition and the comparative composition to form a coating film, and then using the SPECTROPHOTOMETER CM-3700d manufactured by Minolta Co., Ltd., and the spectral value measured by baking in an oven at 230 ° C for 30 minutes, And the spectral value measured after baking in an oven at 230 ° C for 2 hours was evaluated by ΔE*ab, and the following results were obtained.

As can be seen from Table 1, the light-shielding pattern of the embodiment showed heat resistance similar to that of the comparative example, but compared with the comparative form, it was confirmed that the overall pattern property and visibility were good.

However, in the case of the comparative form, it was confirmed that the visibility was significantly inferior to that of the embodiment, and in particular, Comparative Example 5 using a white pigment had the worst visibility.

no

Fig. 1 is a schematic perspective view of a mobile phone to which a touch panel is applied.

Claims (8)

A photosensitive resin composition for forming a non-display portion light-shielding pattern, comprising: a pearl pigment-containing coloring agent (A), an alkali-soluble binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator ( D) and a solvent (E), wherein the aforementioned pearl pigment comprises the amount of the composition in an amount of 0.2 to 2% by weight based on the total weight of the composition, based on the solid content. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the first aspect of the invention, wherein the pearl pigment has an average particle diameter of 5 to 15 μm. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the first aspect of the invention, wherein the pearl pigment comprises a reflective layer core portion and a high refractive index layer coated on the core portion. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the third aspect of the invention, wherein the core portion of the reflective layer is mica, sericite, talc, kaolin, bentonite clay mineral, platy titanium dioxide, At least one of a group consisting of platy ceria, platy alumina, boron nitride, barium sulfate, and platy titanium dioxide/ceria oxide. The photosensitive resin composition for forming a non-display portion light-shielding pattern according to the third aspect of the invention, wherein the reflective layer core portion comprises titanium dioxide (TiO ₂ ), zirconium dioxide (ZrO ₂ ), and trioxide Any one selected from the group consisting of strontium (Sb ₂ O ₃ ), zinc sulfide (ZnS), tin dioxide (SnO ₂ ), and zinc oxide (ZnO). A window substrate having a non-display portion, wherein the non-display portion is formed by forming a non-display portion light-shielding pattern photosensitive resin composition according to any one of claims 1 to 5. A touch screen panel having a window substrate as described in claim 6 of the patent application. An image display device comprising the touch screen panel according to claim 7 of the patent application.