KR102028486B1 - A frontal light-shielding layer of a display device and a display device having the frontal light-shielding layer - Google Patents

Abstract

The present invention has a structure in which a colored coating film 1, a reflective brightness improving coating film 2 and a colored coating film 3 are sequentially stacked on a transparent substrate, and the colored coating film 1 and the colored coating film 3 are reflected brightness. A display including a front light shielding layer and the front light shielding layer of a display device having a refractive index larger than that of the enhancement coating film (2), wherein the colored film (1) has a higher refractive index and higher brightness than the color coating film (3). Provide the device.

Description

Front light shielding layer of a display device and a display device including the same {A FRONTAL LIGHT-SHIELDING LAYER OF A DISPLAY DEVICE AND A DISPLAY DEVICE HAVING THE FRONTAL LIGHT-SHIELDING LAYER}

The present invention relates to a display device including the front light blocking layer of the display device and the front light blocking layer.

In general, the front edges of display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), organic light emitting diodes (OLEDs), and active matrix organic light emitting diodes (AMOLEDs) reduce reflectance to improve display visibility. A bezel part, which is a front shielding layer of a display device, is formed to perform a function of shielding light from the inside of the display, increasing contrast ratio, and preventing the inside of the display from being visible. As a material of the bezel part, a black coating composition is used in many functional aspects, but recently, a coating composition having various colors is used in consideration of various tastes and aesthetics of a display.

By the way, when the coating material of a light color having a low light shielding rate such as white, pink, etc. is used as the coating material of the bezel part, since the inside of the display is easily exposed through the bezel part, under the coating layer formed of the coating material of the light color The bezel portion is formed by further forming a coating layer of gray or black color.

However, in the case of forming the bezel part as a multilayer coating layer in this way, the optical density (OD) is increased by the coating layer of the gray or black color of the lower layer, so that the light shielding rate is improved, but the transmittance of the coating layer of the bright color of the upper layer is higher, The problem arises that the coating layer of gray or black color is seen. Therefore, in order to improve such a point, a method of forming a coating layer having a bright color on the upper layer as a thick film, increasing the reflectance, and the like have been considered. However, forming a coating layer with a thick film has disadvantages such as a large amount of material consumption and reduced work efficiency, and has not found a clear solution by increasing the reflectance.

The present invention, to solve the problems of the prior art as described above,

It is an object to provide a front light shielding layer of a display device formed of various colors of high quality by controlling the transmittance and the reflectance to improve the optical density (O.D.) and the sharpness of the color.

In addition, an object of the present invention is to provide a display device comprising the front light shielding layer.

The present invention,

It has a structure in which the colored coating film 1, the reflection brightness improving coating film 2 and the coloring paint film 3 are sequentially stacked on the transparent substrate,

The colored film 1 and the colored film 3 has a larger refractive index than the reflective film for improving the brightness 2, the colored film 1 is characterized in that the refractive index is larger than the colored film 3 and the brightness is higher A front light shielding layer of a display device is provided.

In addition, the present invention,

It provides a display device comprising the front light shielding layer.

The front light shielding layer of the display device of the present invention can be formed in various colors of high quality by controlling the light transmittance and the reflectance to improve the optical density (O.D.) and the sharpness of the color.

In addition, the display device of the present invention including the front light shielding layer provides excellent design characteristics.

The present invention,

It has a structure in which the colored coating film 1, the reflection brightness improving coating film 2 and the coloring paint film 3 are sequentially stacked on the transparent substrate,

The colored film 1 and the colored film 3 has a larger refractive index than the reflective film for improving the brightness 2, the colored film 1 is characterized in that the refractive index is larger than the colored film 3 and the brightness is higher A front light blocking layer of a display device.

The front light shielding layer of the display device of the present invention is characterized by introducing a coating film 2 for improving the reflection luminance between the colored coating film 1 and the colored coating film 3. That is, the optical film (OD) of the front light-shielding layer and the sharpness of the color are introduced by introducing a reflective film for improving the brightness of the reflective film 2 having a large refractive index difference between the colored film 1 and the colored film 3. (Whiteness (WI), etc.) is increased.

In the above, it is preferable that the reflective brightness improving coating film 2 is a transparent coating film.

In the present invention, it is more preferable that the refractive index difference between the colored coating film 1 and the reflective brightness improving coating film 2 is 0.5 to 2.0 for improving the optical density (O.D.) and the sharpness of the color of the front light shielding layer.

As a specific example of the front light shielding layer of the display apparatus of this invention, the colored coating film 1 is a white coating film, and the coloring coating film 3 is a black or gray coating film. In addition, the coloring film 1 may be formed of a coating film of various colors.

The transparent substrate used in the present invention may be a glass substrate, in particular a tempered glass substrate, or may be a transparent polymer substrate.

Hereinafter, the components of the coating film constituting the front light shielding layer of the display device will be described by way of example.

The coating composition of the same or similar composition may be used for forming the colored film 1, the reflective brightness improving film 2 and the colored film 3 of the present invention except for the difference depending on the inclusion and type of the colorant. . Of course, it is also possible to use different coating compositions. Hereinafter, the components of the coating composition which can be commonly used will be described by way of example.

(A) colorant

In the case of the coloring film 1 and the coloring film 3, a pigment or dye known in the art can be employed according to the desired color to constitute the colorant.

In the case of a white front light shielding layer (bezel), the colored coating film 1 is also formed in white, and as the colorant, titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, calcium carbonate, alumina oxide pigment, etc. may be used. have. C.I. As the pigment number, white 4, 5, 6, 6: 1, 7, 18, 18: 1, 19, 20, 22, 25, 26, 27, 28, 32, and the like may be used. Preferably in consideration of the reflection efficiency and the whiteness in the white pigment C.I. Pigment White 6 and C.I. Pigment White 22 may be used.

In particular, TiO ₂ included in the CI Pigment White 6 may be used as an effective white colorant because the price is low and the refractive index is high and the reflectivity is excellent.

The TiO ₂ preferably has a rutile structure. TiO ₂ having a rutile structure has excellent whiteness and can therefore be preferably used.

TiO _{2, which} is the white pigment, may be subjected to surface treatment using a resin treatment, a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound, an atomization treatment or an impurity by a sulfate atomization method, or the like. The cleaning treatment with an organic solvent, water, or the like for removing the ions may be performed, or the ionic impurities may be removed by an ion exchange method.

The TiO ₂ is a surface of SiO ₂ , Al ₂ O ₃ And at least one selected from the group consisting of ZrO ₂ may be preferably used.

More preferably, SiO ₂ , Al ₂ O ₃ And those sequentially surface treated with ZrO ₂ may be used.

Even more preferably the outermost surface of TiO ₂ surface-treated above Surface treated with organic material can be used. For example, trimethyl propane (TMP), pentaerythritol, or the like may be used as the organic material. Coating the surface by coating TiO ₂ with a single molecule layer of low polarity using the above components lowers the energy required for TiO ₂ dispersion and prevents TiO _{2 from} being compressed and aggregated.

The surface treatment of TiO ₂ as described above while lowering the photocatalytic activity of the TiO ₂ improves the reflected luminance characteristic. In particular, when the surface treatment of each of SiO ₂ , Al ₂ O ₃ , and ZrO ₂ is applied to TiO ₂ , reliability such as heat resistance and chemical resistance is improved. The surface treatment may be treatment by encapsulation.

The TiO ₂ surface treated is preferably 85 to 95% by weight of the TiO ₂ core. When the surface of the TiO ₂ core is treated within the above range, the whiteness is excellent and the reflection luminance is excellent.

Specific examples of the TiO ₂ include R-101, R-102, R-103, R-104, R-105, R-350, R-706, R-794, R-796, which are commercially available from DuPont. TS-6200, R-900, R-902, R-902 +, R-931, R-960, and the like, and also Huntman's R-FC5, TR81, TR88 and ISK CR-57 etc. can be illustrated.

When the colored coating film 1 has a color, the pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyrantrones (pyranthrone) pigments, diketopyrrolopyrrole pigments and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide. In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) number of Although a pigment is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

CI Pigment Black 1 and 7 etc

C.I. exemplified above. Among pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigments selected from Pigment Green 58 may be preferably used.

As the coloring film 3, a black coating film or a gray coating film is mainly employed. In this case, carbon black or the like may be preferably used as the coloring agent.

The coloring agent (A) is contained in the solid content in the coating composition of the present invention 10 to 80% by weight based on the total weight, more preferably contained in 30 to 70% by weight. When the colorant is included in the above range, it is preferable because the color is excellent in the sharpness of the color when forming the front light shielding layer of the display device, and exhibits excellent reflection luminance.

Solid content in this invention means the component except a solvent.

(B) resin

As the resin used in the present invention, those known in the art may be used, and examples of specific resins are as follows:

The resin (B) may be made based on the structural units of the following Chemical Formulas 1 to 4:

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

In the resin, the reactants of Chemical Formulas 1 to 4 may be included in an amount of 3 to 80 mol%, more preferably 5 to 70 mol%, based on the mole fraction with respect to the total number of moles of the resin (B). When the structural unit is included in the above range, the coating composition is excellent in sensitivity and adhesion, so that no peeling of the pattern occurs during the developing process, and exhibits excellent solvent resistance.

Alkali-soluble resins having the structural units of Formulas 1 to 4 may be prepared by polymerization of various polymerizable compounds.

Formula 1 to 4 of the resin (B) is copolymerizable with another monomer having a copolymerizable unsaturated bond, specific examples of the monomer having a copolymerizable unsaturated bond are styrene, vinyltoluene, α-methylstyrene, p Chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl Aromatic vinyl compounds such as ether, m-vinylbenzyl glycidyl ether and p-vinyl benzyl glycidyl ether; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; (meth) acrylamide, Unsaturated amide compounds such as N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds.

The compounds exemplified above may be used alone or in combination of two or more thereof.

Resin (B) according to the present invention may be used by further mixing a variety of other known resins generally used in the art as needed.

It is preferable that the resin has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, and preferably in the range of 5,000 to 50,000. If the weight average molecular weight of the resin is less than 3,000 or more than 100,000, there is a disadvantage in that the film reduction is not prevented during the development, so that the omission of the pattern portion occurs or the development does not occur.

The acid value of the said resin (B) is 50-150 (KOHmg / g), Preferably it is 60-140 (KOHmg / g), More preferably, it is 80-135 (KOHmg / g), Most preferably Preferably 80 to 130 (KOH mg / g). When the acid value of the said resin (B) is 50-150 (KOHmg / g), since the solubility to a developing solution improves and a residual film rate improves, it is preferable.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

The resin (B) may be included in 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of solids of the coating composition of the present invention. When the content of the resin (B) is included in the above range, the solubility of the developing solution is sufficient, so that pattern formation is easy, and the reduction of the film portion of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is good. Do.

(C) Polymerizable  compound

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by the action of a photopolymerization initiator described below, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional photopolymerizable compound. Compounds and the like.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School).

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like; commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nipbon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagakusa).

Specific examples of the trifunctional or higher polyfunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxysilane Tied dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are commercially available products such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD. DPHA-40H (Nippon Kayaku).

Among the polymerizable compounds (C) exemplified above, trifunctional or higher functional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.

The polymeric compound (C) illustrated above can be used individually or in combination of 2 types or more, respectively.

The polymerizable compound (C) is preferably contained in 5 to 45% by weight, more preferably in the 7 to 45% by weight based on the total solids weight of the coating composition of the present invention. When the said polymeric compound (C) is contained in said range, since the intensity | strength and smoothness of a pixel part become favorable, it is preferable.

(D) Polymerization initiator

The polymerization initiator (D) can be used without particular limitation as long as it can polymerize the polymerizable compound (C).

In particular, the polymerization initiator (D) may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, or a thioxanthone compound in view of polymerization characteristics, initiation efficiency, or price. Preference is given to using at least one compound selected from the group consisting of.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- Butyl peroxycarbonyl) benzophenone, 2, 4, 6-trimethyl benzophenone, etc. are mentioned.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine or 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4 ', 5,5'- tetraphenyl- 1,2'-biimidazole or a 4,4', 5,5 'position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferably Can be used.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF Corporation are typical examples of commercially available products.

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

Moreover, the polymerization initiator of that excepting the above can also be used together in the range which does not impair the effect of this invention. For example, a peroxide type or a sulfide type compound, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively. Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid A methyl or titanocene compound, etc. can be used together further as a photoinitiator.

In addition, the polymerization initiator (D) may further include a polymerization initiation aid (D-1) in order to improve the reactivity of the coating composition of the present invention. As said polymerization start adjuvant (D-1), 1 or more types of compounds chosen from the group which consists of an organic sulfur compound which has an amine compound, a carboxylic acid compound, and a thiol group, for example can be used preferably.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ) Or 4,4'-bis (diethylamino) benzophenone can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercapto Butyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) or tetraethylene glycol bis (3-mercaptopropionate) Can be mentioned.

The polymerization initiator (D) may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the sum of the resin (B) and the photopolymerizable compound (C). When the polymerization initiator (D) is included in the above-mentioned range, the coating composition is highly sensitive, and thus the reaction time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the coating film portion formed using the composition under the above-described conditions and smoothness on the surface of the coating film portion can be improved.

In addition, when the polymerization initiation aid (D-1) is further used, it is preferable to use the same content range as the polymerization initiator (D), and when used in the above-described content, the sensitivity of the coating composition is higher, and the composition It provides an effect that the productivity of the coating film formed by using the.

(E) solvent

If the solvent (E) is effective to dissolve the other components included in the coating composition, can be used without particular limitation to the solvent used in the usual coating composition, especially ethers, aromatic hydrocarbons, ketones, alcohols, esters Or amides are preferable.

Specifically, the solvent (E) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di Ethers such as propyl ether and dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-meth Methoxybutyl acetate, 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 diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ-buty Rockactone, etc. And esters thereof.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lac Tate, butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc. can be used.

The solvent (E) mentioned above can be used individually or in mixture of 2 or more types, respectively.

The solvent (E) may be included in 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the coating composition of the present invention. When the solvent (E) is included in the above-described range, the coating property becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater) or inkjet. Provide effect.

The front light blocking layer (bezel portion) of the display device of the present invention may be formed by forming a desired pattern through a printing process or an offset process and performing a curing process. Alternatively, the front light shielding layer may be prepared by applying a coating composition on a substrate, curing, and developing the substrate by the following method to form a pattern.

The latter method will be described in detail. First, the photosensitive coating composition is applied to a substrate (usually a glass, in particular, tempered glass or plastic substrate) or a layer of a colored coating film formed first, and then heated and dried to remove volatile components such as a solvent and smooth it. Get a coat.

As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. After coating, heating and drying under reduced pressure or heating under reduced pressure to volatilize volatile components such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 0.1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.

G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation dose of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. The desired pattern can be formed when the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.

These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the compound in the developing solution is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.

The content of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it washes with water and can also carry out post-baking for 10 to 60 minutes at 150-230 degreeC as needed.

Using the coating composition of the present invention, a coating film having a pattern can be formed on the top of the substrate or the top of the colored coating film through the above steps. This pattern can be usefully used as a front light shielding layer (bezel portion) of a display device.

In addition, the present invention provides a display device comprising a front light shielding layer of the display device.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Synthesis Example  1: Synthesis of Resin (B)

Preparing a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube; 40 parts by weight of a mixture of 50,50 molar ratio of 3,4-epoxytricyclodecane-8-yl (meth) acrylate and 3,4-epoxytricyclodecane-9-yl (meth) acrylate in a monomer dropping lot 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Then stirred and mixed to prepare a monomer dropping lot; 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added to the chain transfer agent dropping tank to prepare a chain transfer agent drop lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were added dropwise from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours to obtain a resin (B) having a solid acid value of 75 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured under the following conditions using the GPC method.

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Production Example  1 to Production Example  4: Preparation of Coating Composition for Coating Film Formation

To prepare a coating composition by mixing the components shown in Table 1 according to the composition ratio.

Pigment
Suzy Polymerizable compound Polymerization initiator solvent Kinds content Preparation Example 1 Titanium oxide 50 25 23 2 200 Preparation Example 2 - - 55 40 5 200 Preparation Example 3 Carbon black 40 30 28 2 200 Preparation Example 4 Titanium Oxide / Carbon Black 30/10 30 28 2 200

(Unit: weight%)

Resin: Use of Resin Prepared in Synthesis Example 1

Polymerizable compound: KAYARAD DPHA (manufactured by Nippon Kayaku)

Polymerization initiator: Irgacure OXE-02 (BASF)

Solvent: Propylene Glycol Monomethyl Ether Acetate

Example  1: front of the display device Shading  Produce

A glass substrate (5 cm × 5 cm, Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coating composition prepared in Preparation Example 1 was spin coated onto a glass substrate, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask is 50 μm, and the light is irradiated with an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; Topcon Co., Ltd.). It was. At this time, radiation of ultra-high pressure mercury lamp was used for light irradiation, and a photomask having a pattern having a square light-transmitting portion of 3 cm × 3 cm was used on the same plane. After light irradiation, the coating film was developed by immersing the aqueous coating solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds, and then washed with water in an oven for 20 minutes at 220 ° C. to prepare a substrate. . The thickness of the white coating film was measured to be 6㎛.

Using the substrate to which the white coating film was introduced, spin-coated the composition prepared in Preparation Example 2 on the white coating film, and then dried at 90 ° C. for 3 minutes using a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and light was emitted at an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Investigate. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After irradiation with light, the coating film was developed by immersion for 100 seconds at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. After washing with water, the substrate was dried at 220 ° C. for 20 minutes. Made. At this time, the thickness of the formed reflective brightness improvement coating film was measured to be 0.5 micrometer.

After cooling the substrate to which the coating film for improving the reflection brightness was introduced on the surface of the white coating film was cooled to room temperature, the composition prepared in Preparation Example 3 was spin coated, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and the light was exposed at an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Was investigated. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds for development. After washing with water, post-baking was carried out at 220 ° C. for 20 minutes in an oven. A 3 μm black coating was formed to prepare the front light shielding layer of the display device.

Example  2: front of the display device Shading  Produce

A glass substrate (5 cm × 5 cm, Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. The coating composition prepared in Preparation Example 1 was spin coated onto a glass substrate, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask is 50 μm, and the light is irradiated with an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; Topcon Co., Ltd.). It was. At this time, radiation of ultra-high pressure mercury lamp was used for light irradiation, and a photomask having a pattern having a square light-transmitting portion of 3 cm × 3 cm was used on the same plane. After light irradiation, the coating film was developed by immersing the aqueous coating solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds, and then washed with water in an oven for 20 minutes at 220 ° C. to prepare a substrate. . The thickness of the white coating film was measured to be 6㎛.

The coating composition prepared in Preparation Example 2 was spin coated on the white coating film using the substrate on which the white coating film was introduced, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and light was emitted at an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Investigate. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After light irradiation, the coating film was developed by immersing the coating film for 25 seconds at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by washing for 20 minutes at 220 ° C. in an oven after washing with water to prepare a substrate. . At this time, the thickness of the formed reflective film for improving the brightness was measured to be 2 m.

After cooling the substrate into which the coating film for improving the reflection brightness was introduced on the surface of the white coating film was cooled to room temperature, the coating prepared in Preparation Example 4 was spin coated, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and the light was exposed at an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Was investigated. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After light irradiation, the coating film was developed by immersing the coating film at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by post-baking at 220 ° C. for 20 minutes in an oven after washing with water. A 3 μm gray film was formed to prepare a front light shielding layer of the display device.

Comparative example  1: front of the display device Shading  Produce

A glass substrate (5 cm X 5 cm, Eagle 2000; manufactured by Corning) was washed sequentially with a neutral detergent, water and alcohol, and dried. The coating composition prepared in Preparation Example 1 was spin coated onto a glass substrate, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and light was emitted at an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Investigate. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After light irradiation, the coating film was developed by immersing the coating film at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by washing for 20 minutes at 220 ° C. in an oven after washing with water. A light shielding layer was formed. The thickness of the white coating film was measured to 6㎛.

Comparative example  2: front of the display device Shading  Produce

The coating composition prepared in Preparation Example 3 was spin coated on the white coating film of the front light shielding layer prepared in Comparative Example 1, and then dried at 90 ° C. for 3 minutes using a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and light was emitted at an exposure dose (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK: Topcon Co., Ltd.). Investigate. At this time, the radiation of the ultra-high pressure mercury lamp was used for the irradiation of light, the photomask is a 3cm x 3cm photomask in which a pattern having a square light transmitting part is formed on the same plane. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 100 seconds at 25 ° C for 100 seconds. The black coating layer was formed to manufacture the front light blocking layer of the display device.

Comparative example  3: front of the display device Shading  Produce

The coating composition prepared in Preparation Example 4 was spin coated on the white coating film of the front light shielding layer prepared in Comparative Example 1, and then dried at 90 ° C. for 3 minutes in a clean oven. After cooling the dried substrate to room temperature, the distance from the quartz glass photomask was 50 μm, and light was emitted at an exposure amount (365 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Investigate. At this time, radiation of ultra-high pressure mercury lamp was used for irradiation of light, and a photomask in which a pattern having a square light-transmitting portion was introduced on the same plane as a photomask was 3 cm × 3 cm. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 100 seconds for development, and washed with water in an oven at 220 ° C. for 20 minutes to give a thickness of 3 μm. The gray coating film was formed to manufacture the front light shielding layer of the display device.

Test Example : Optical density  And whiteness assessment

Examples of the front light blocking layer of the display device manufactured in Examples 1 to 2 and Comparative Examples 1 to 3 Optical density and whiteness were measured by the following method, and the results are shown in Table 2 below.

[ Optical density  How to measure]

Optical density (OD) was measured using an X-rite 361T model and the prepared light shielding layer samples were measured and filled in without further processing.

[Whiteness Evaluation Method]

Whiteness was calculated using the value measured in MINOLTA SPECTROPHOTOMETER CM-3700d using the following equation. That is, the reflectance was measured five times in each D65 light source for each sample, and the whiteness was calculated by the following equation using the average value thereof, and is shown in Table 2 below.

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 O.D. 4.87 1.74 0.75 4.68 1.48 W.I. 82.4 84.4 85.1 62.2 78.8

O.D .: Optical density

W.I .: White Index = Y + 800 (Xn-x) +1700 (yn-y)

As shown in Table 2, when only the white coating film is introduced into the glass substrate in Comparative Example 1, W.I. It can be seen that high. But O.D. The very low value indicates the problem of seeing internal components when the display device is manufactured. Therefore, as in Comparative Example 2, the black coating film was introduced together with the white coating film to produce O.D. It is possible to increase the shielding property by increasing the value. However, in this case, it is understood that the W.I. is lowered because the black coating film on the back side is high due to the high transmittance of the white coating film. In addition, as in Comparative Example 3, when a gray (gray) coating film is introduced, W.I. You may not lower the value much, but O.D. It can be seen that the value does not increase sufficiently.

As in Examples 1 and 2 of the present invention, when there is a coating film for improving the reflection brightness between the white coating film and the coloring coating film (black or gray coating film), O.D. Value and W.I. It can be seen that the value increases (comparison of Example 1 and Comparative Example 2; and comparison of Example 2 and Comparative Example 3).

Claims (8)

It has a structure in which the colored coating film 1, the reflection brightness improving coating film 2 and the coloring paint film 3 are sequentially stacked on the transparent substrate,
The colored film (1) and the colored film (3) has a larger refractive index than the reflective film for improving the brightness 2, the colored film (1) is characterized in that the refractive index is larger than the colored film 3 and the brightness is higher ,
The reflective film for improving brightness is produced by applying a coating composition on a substrate, curing and developing to form a pattern, the front light shielding layer of the display device. The front light shielding layer of a display device according to claim 1, wherein said reflective brightness improving film (2) is a transparent coating film. The front light shielding layer of a display device according to claim 1, wherein a difference in refractive index between the colored coating film (1) and the reflective brightness improving coating film (2) is 0.5 to 2.0. The front light shielding layer of a display device according to claim 1, wherein the colored coating (1) is a white coating and the colored coating (3) is a black coating or a gray coating. The front shielding layer of claim 1, wherein the transparent substrate is a glass substrate. The method according to claim 4, wherein the colored coating 1 is TiO ₂ as a pigment The front light blocking layer of the display device comprising a. The method according to claim 6, wherein the coloring film 3 is carbon black as a pigment The front light blocking layer of the display device comprising a. A display device comprising a front shielding layer of a display device according to any one of claims 1 to 7.