KR102226800B1 - Photosensitive resin composition for bezel pattern, manufacturing method for bezel pattern of display panel and bezel pattern of display panel using the same - Google Patents

Abstract

The present invention relates to a photopolymerizable composition for forming a bezel pattern comprising a colorant, an epoxy monomer, an oxetane monomer, a photopolymerization initiator, and a solvent having a boiling point of 190 to 280°C, a method for producing a bezel pattern of a display substrate using the same, and a bezel pattern using the same. About.

Description

A photopolymerizable composition for forming a bezel pattern, a method of manufacturing a bezel pattern of a display substrate using the same, and a bezel pattern manufactured by the same (PHOTOSENSITIVE RESIN COMPOSITION FOR BEZEL PATTERN OF DISPLAY PANEL AND BEZEL PATTERN OF DISPLAY PANEL USING THE SAME }

The present invention relates to a photopolymerizable composition for forming a bezel pattern, a method of manufacturing a bezel pattern of a display substrate using the same, and a bezel pattern manufactured thereby.

In display devices such as TVs and monitors, circuits that apply electrical signals to operate the device are located on four sides of the inside of the device. Since circuits made of metals such as copper or aluminum reflect external light, a bezel is required to block this. Conventionally, a separate plastic structure case has been used, but recently, a method of directly forming a bezel pattern on a touch screen or a thin film transistor substrate by using a printing method such as screen printing or inkjet has been used.

When forming a bezel pattern using such an inkjet method, it is easy to apply a low or high thickness, a high resolution pattern can be formed, and a low viscosity material can be applied.

However, when using such an inkjet method, if the evaporation rate of ink is not sufficiently slow, the fine ink droplets formed on the surface of the fine nozzles of the inkjet head tend to be dried as shown in FIG. 1. Dried fine ink droplets become solid and may cause nozzle clogging or nozzle failure.

Accordingly, in the prior art, in order to suppress the evaporation rate of the ink composition, a solvent having a low boiling point is removed, a solvent having a high boiling point is used, or a solvent-free composition composed of only reactive components having a high boiling point is used as shown in FIG. 2. When a solvent having a high boiling point is used, the drying problem can be solved, but since evaporation is too slow, there is a problem that the residual solvent remains in the film even after curing, resulting in poor curing speed and film properties. In addition, when only a reactive component is formed, it is difficult to lower the viscosity of the ink composition, and since there is no solvent evaporation accompanying the curing, the thickness of the film cannot be lowered, so that sufficient shielding power cannot be obtained at a low thickness.

Therefore, compared to the conventional bezel composition, it is necessary to develop a composition having a low evaporation rate on the surface of the inkjet head and not having poor curing speed and film properties.

KR 10-2013-0112003 A

In order to solve the problems of the prior art, the present invention forms a bezel pattern using a photopolymerizable composition for forming a bezel pattern that does not decrease the curing reaction rate while having a high boiling point, so that the film properties remain in the thin film during the process. It is an object to form a bezel pattern that does not exhibit deterioration and curing inhibition.

In order to solve the above problem,

The present invention provides a photopolymerizable composition for forming a bezel pattern comprising a colorant, an epoxy monomer, an oxetane monomer, a photoinitiator, and a solvent having a boiling point of 190 to 280°C.

In addition, the present invention, using the photopolymerizable composition for forming a bezel pattern, forming a bezel pattern on a substrate; And curing the bezel pattern. It provides a method of manufacturing a bezel pattern for a display substrate comprising a.

In addition, the present invention provides a bezel pattern for a display substrate formed on a substrate by curing the photopolymerizable composition for forming a bezel pattern.

In addition, the present invention provides a display substrate including the bezel pattern for the display substrate.

According to the present invention, since the photopolymerizable composition for forming a bezel pattern that has a high boiling point and does not decrease the curing reaction rate is used, in forming the bezel pattern, it remains in the thin film during the process, thereby reducing film properties and inhibiting curing. It has the advantage of not doing it.

1 is a schematic diagram showing an ink jet process according to the prior art.
2 is a schematic diagram showing another conventional inkjet process.

Hereinafter, the present invention will be described in more detail.

The present invention provides a photopolymerizable composition for forming a bezel pattern comprising a colorant, an epoxy monomer, an oxetane monomer, a photoinitiator, and a solvent having a boiling point of 190 to 280°C.

In addition, the photopolymerizable composition for forming a bezel pattern of the present invention may further include any one or more selected from the group consisting of a surfactant, an adhesion enhancer, a diluent, and a photosensitizer.

In the photopolymerizable composition for forming a bezel pattern, a radical polymerization type compound and a cationic polymerization type compound may be mainly used. In the case of a radical polymerizable compound, it is not suitable for hardening of a thin film because it suffers from curing failure due to oxygen, and because of its large curing shrinkage, it has low adhesion to a glass substrate and is not suitable for forming a bezel pattern. On the other hand, in the case of a cationic polymerization type compound, since the curing shrinkage is generally low and the effect of oxygen is small, it is advantageous for curing the thin film.

The photopolymerizable composition for forming a bezel pattern used in the present invention contains an epoxy monomer as a cationic curing component. The epoxy monomer is specifically selected from a bisphenol type epoxy monomer, a novolak type epoxy monomer, a glycidyl ester type epoxy monomer, a glycidyl amine type epoxy monomer, a linear aliphatic epoxy monomer, a biphenyl type epoxy monomer, and an alicyclic epoxy compound. It may be one or a mixture of two.

The alicyclic epoxy compound may mean a compound including one or more epoxidized aliphatic cyclic groups.

In the alicyclic epoxy compound containing an epoxidized aliphatic cyclic group, the epoxidized aliphatic cyclic group refers to an epoxy group bonded to the alicyclic ring, for example, 3,4-epoxycyclopentyl group, 3,4-epoxy Cyclohexyl group, 3,4-epoxycyclopentylmethyl group, 3,4-epoxycyclohexylmethyl group, 2-(3,4-epoxycyclopentyl)ethyl group, 2-(3,4-epoxycyclohexyl)ethyl group, 3- Functional groups, such as a (3,4-epoxycyclophenyl)propyl group or a 3-(3,4-epoxycyclohexyl)propyl group, can be illustrated. In the above, the hydrogen atom constituting the alicyclic ring may be optionally substituted with a substituent such as an alkyl group. As the alicyclic epoxy compound, for example, a compound specifically exemplified below may be used, but the epoxy compound that may be used is not limited to the following types.

For example, dicyclopentadiene dioxide, cyclohexene oxide, 4-vinyl-1,2-epoxy-4-vinylcyclohexene, vinylcyclohexene dioxide, limonene monooxide, limonene dioxide, (3,4-epoxycyclohexyl)methyl- 3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis(2,3-epoxycyclopentyl) ether, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4- Epoxy-6-methylcyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexane Carboxylate, ethylene glycol bis (3,4-epoxycyclohexyl) ether, 3,4-epoxycyclohexenecarboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Daicel Corporation Celoxide 8000 manufactured by the company can be used.

The content of the epoxy monomer is preferably 5 to 40% by weight, more preferably 10 to 30% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. When it exceeds 40% by weight, the viscosity of the composition increases, and when it is less than 5% by weight, the curing sensitivity decreases.

The photopolymerizable composition for forming the bezel pattern includes an oxetane monomer as another cationic polymerizable monomer.

The oxetane monomer is a compound having a four-membered cyclic ether group in its molecular structure, and may function to lower the viscosity of the cationic cured ink composition (for example, less than 50 cPs at 25° C.).

Specifically, 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl) Oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-cyclohexyloxymethyl oxetane or Phenol novolac oxetane and the like may be exemplified. Examples of the oxetane compound include "Allonoxetane OXT-101", "Allonoxetane OXT-121", "Allonoxetane OXT-211", "Allonoxetane OXT-221" by Toagosei Co., Ltd., or "Alonoxetane OXT-212" or the like can be used. These can be used alone or in combination of two or more.

The content of the oxetane monomer is preferably 20 to 70% by weight, more preferably 40 to 60% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. When it exceeds 70% by weight, the curing sensitivity is low, and when it is less than 20% by weight, the viscosity increases and the coatability decreases.

In addition, the oxetane monomer of the present invention can be used including an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings. When the oxetane compound having one oxetane ring and the oxetane compound having two oxetane rings are used together, the viscosity and flexibility of the film can be controlled. When two types of oxetane compounds are used together as described above, an oxetane compound having one oxetane ring: The content range of the oxetane compound having two oxetane rings is in the range of 1:16 to 1:3. It is preferable to use.

The ink composition of the present invention contains a compound that produces cationic species or Bronsted acid by irradiation with ultraviolet rays as a cationic photopolymerization initiator, for example, iodonium salt or sulfonium salt, but is limited thereto. It does not become.

The iodonium salt or sulfonium salt causes a curing reaction in which a monomer having an unsaturated double bond contained in the ink reacts to form a polymer in the UV curing process, and a photosensitizer may be used depending on polymerization efficiency.

For example, the photopolymerization initiator may be one having an anion represented by _{SbF 6} -, AsF ₆ -, BF ₆ -, (C ₆ F ₅ ) ₄ B-, PF ₆ -or RfnF _{6-n, but is limited thereto.} It does not become.

The photopolymerization initiator is preferably included in an amount of 0.5 to 10% by weight based on the total weight of the photopolymerizable composition for forming a bezel pattern. If the content of the photopolymerization initiator is less than 0.5% by weight, the curing reaction is not sufficient, and if it is more than 10% by weight, all of them are not dissolved or the viscosity increases, resulting in a decrease in coating properties.

The ink composition may include a solvent having a boiling point of 190 to 280°C in order to improve the coating property by decreasing the viscosity of the ink to increase fluidity, and to prevent a decrease in the light-shielding density per unit thickness, more preferably a boiling point. It may contain a solvent of 200 ~ 260 ℃. In the present invention, by using a solvent having a boiling point of 190 to 280°C as described above, the nozzle does not dry out during inkjet printing and does not cause a decrease in curing speed, so that a problem may not occur in curing of the coating film.

In the present invention, as the solvent, any one or more selected from the group consisting of alcohols, glycols, and glycol-based ethers having a boiling point of 190 to 280°C may be used.

The glycol-based ether having a boiling point of 190 to 280°C may be an alkylene glycol alkyl ether having C1 to C6 carbon atoms in the alkyl glycol part, more preferably ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl Any one or more selected from the group consisting of ether, tetraethylene glycol alkyl ether, propylene glycol alkyl ether, dipropylene glycol alkyl ether, and glycol dialkylene ether may be used, and most preferably, the number of carbon atoms in the alkyl ether portion is C1~ A monoalkyl ether having one C4 alkyl group or a dialkyl ether having two C1 to C4 alkyl groups in the number of carbon atoms in the alkyl ether moiety may be used.

The content of the solvent is preferably 1 to 40% by weight based on the total weight of the photopolymerizable composition for forming a bezel pattern. If the content of the solvent is more than 40% by weight, curing sensitivity is lowered.

The photopolymerizable composition for forming the bezel pattern includes a colorant.

The colorant may be used in the form of a pigment dispersion containing one or more pigments, dyes, or mixtures thereof, and is not particularly limited as long as it can express a color according to need.

As a specific example of the present invention, carbon black, graphite, metal oxide, organic black pigment, etc. may be used as the pigment.

Examples of carbon black include Cysto 5HIISAF-HS, Cysto KH, Cysto 3HHAF-HS, Cysto NH, Cysto 3M, Cysto 300HAF-LS, Cysto 116HMMAF-HS, Cysto 116MAF, Cysto FMFEF-HS. , Systo SOFEF, Systo VGPF, Systo SVHSRF-HS and Systo SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, # 2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, # 3030, #3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (Daegu Corporation); RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (Colombia Carbon Co., Ltd.), or mixtures thereof.

As the organic black pigment, aniline black, lactam black, or perylene black series may be used, but the present invention is not limited thereto.

In the present invention, the photopolymerizable composition for forming a bezel pattern is cured by irradiation with ultraviolet (for example, 250 or 450 nm), more preferably, long-wavelength ultraviolet (for example, 360 nm to 410 nm), and has a certain level of OD (Optical Density). It characterized in that it has. To this end, the content of the colorant is preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the total weight of the photopolymerizable composition for forming a bezel pattern. When the content of the colorant is less than 1% by weight, an OD of a level applicable to the bezel does not appear, and when the content of the colorant is more than 15% by weight, an excess colorant may not be dispersed in the ink and a precipitate may be formed.

When the content of the colorant is within the above range, the OD value may be maintained in the range of 0.1 to 1.5 per 1.0 μm of film thickness.

The photopolymerizable composition for forming a bezel pattern includes a surfactant that lowers the surface tension of the ink composition in order to exhibit a small taper angle.

Commercially available products may be used as the surfactant, for example, Megafack F-444, F-475, F-478, F-479, F-484, F-550, F-552 manufactured by DIC (DaiNippon Ink & Chemicals). , F-553, F-555, F-570, RS-75 or Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141 and S-145 or Sumitomo 3M's Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 or DuPont's Zonyl FS-300, FSN, FSN-100 and FSO and BYK's BYK-306, BYK-310, BYK-320, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-355, BYK-356, BYK- 358N, BYK-359, BYK-361N, BYK-381, BYK-370, BYK-371, BYK-378, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, BYK-SILCLEAN 3700 and BYK-UV 3570 or Tego's Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370 and Flow 425, etc. I can.

The surfactant is preferably contained in an amount of 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight, based on the total weight of the photopolymerizable composition for forming a bezel pattern. If the content of the surfactant is less than 0.1% by weight, the effect of lowering the surface tension of the composition is not sufficient, so that the composition cannot be uniformly applied when coating the composition on the substrate, and if it exceeds 5.0% by weight, the surfactant is used in excess. There is a problem in that the compatibility and defoaming property of the composition is rather reduced.

The photopolymerizable composition for forming a bezel pattern may further include a photosensitizer to supplement curability in a long wavelength active energy ray.

The photosensitizer is anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxy

Anthracene compounds such as anthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-dimethoxyanthracene; Benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoate, 3,3 -Benzophenone compounds such as dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; Acetophenone; Ketone compounds such as dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; Perylene; Fluorenone compounds, such as 9-fluorenone, 2-chloro-9-prorenone, and 2-methyl-9-fluorenone; Thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone (ITX), diisopropyl thioxanthone, etc. Thioxanthone compounds; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane, etc. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo[2,2,1]heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide; Benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxyethyl-4-(dimethylamino)benzoate; 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanone, 2,6-bis(4-diethylaminobenzal)-4- Amino synergists such as methyl-cyclopentanone; 3,3-carbonylvinyl-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3 -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]-benzo Coumarin compounds such as pyrano[6,7,8-ij]-quinolizin-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene; And 3-methyl-b-naphthothiazoline.

The photosensitizer is preferably contained in an amount of 1 to 200 parts by weight, more preferably in an amount of 10 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator. If it is less than 1 part by weight, it is not possible to expect a synergistic effect of the curing sensitivity at a desired wavelength, and if it is more than 200 parts by weight, there is a problem that the photosensitizer cannot be dissolved and the adhesion and crosslinking density of the pattern are lowered.

The photopolymerizable composition for forming the bezel pattern may further include an adhesion enhancer as an additive.

The film attached to the bezel pattern may contract and expand according to usage conditions such as temperature and humidity, so that stress is applied to the bezel pattern, so that the film and the bezel may fall off the glass substrate. To prevent this, at least one silane-based compound selected from the group consisting of alkoxy silane-based compounds, epoxy silane-based compounds, aminophenyl silane-based compounds, amino silane-based compounds, mercapto silane-based compounds, and vinyl silane-based compounds as adhesion promoters. Excellent results can be obtained when using.

Among these, epoxy silane-based compounds are more preferable as the adhesion promoter of the present invention.

The adhesion promoter is preferably contained in an amount of 0.1 to 15% by weight, more preferably 2 to 10% by weight, based on the total weight of the ink composition. If it is less than 0.1% by weight, it cannot prevent the bezel pattern from peeling off from the glass substrate, and if it is more than 15% by weight, the viscosity of the ink solution increases and the dispersibility is low.

The photopolymerizable composition for forming a bezel pattern used in the present invention spreads within a short time immediately after inkjet printing, exhibits excellent coating properties, and is cured to exhibit excellent adhesive properties. Therefore, when applying the photopolymerizable composition for forming a bezel pattern, it is preferable to install a UV-lamp immediately behind the inkjet head so as to enable curing at the same time as inkjet printing.

The photopolymerizable composition for forming a bezel pattern has a curing dose of 1 to 10,000 mJ/cm 2, preferably 80 to 2,000 mJ/cm 2.

The photopolymerizable composition for forming the bezel pattern is cured by absorbing radiation in a wavelength range of 250 nm to 450 nm, preferably 360 nm to 410 nm.

The photopolymerizable composition for forming a bezel pattern has a viscosity of 1 to 20 mPa·s at 25°C, and thus is suitable for an inkjet process. The photopolymerizable composition for forming a bezel pattern having the above viscosity range is excellent in discharge at a process temperature. The process temperature means a temperature heated to lower the viscosity of the curable ink composition. The process temperature may be 10°C to 100°C, preferably 20°C to 70°C.

In addition, the photopolymerizable composition for forming the bezel pattern, for example, when evaporated in a convection oven at 35°C, may have a residual mass of 85% or more after 2 hours, so that the evaporation rate is low, but the curing rate and film properties are not poor. do.

The upper end of the bezel pattern formed of the photopolymerizable composition for forming the bezel pattern is attached to the upper substrate through an adhesive layer for the upper substrate, and the photopolymerizable composition for forming the bezel pattern includes an acrylic adhesive, a styrene butadiene rubber adhesive, an epoxy adhesive, Since it exhibits excellent adhesion to an upper substrate such as a polyvinyl alcohol-based pressure-sensitive adhesive and a polyurethane-based pressure-sensitive adhesive, when the photopolymerizable composition for forming the bezel pattern is used, it is possible to obtain an effect of improving the adhesion between the bezel pattern and the upper substrate.

The method of manufacturing a bezel pattern for a display substrate of the present invention uses the photopolymerizable composition for forming the bezel pattern.

Specifically, the method of manufacturing a bezel pattern for a display substrate of the present invention includes: a) forming a bezel pattern on a substrate using the photopolymerizable composition for forming a bezel pattern; And b) curing the bezel pattern.

In addition, the method of manufacturing a bezel pattern of a display substrate of the present invention may further include cleaning and drying the substrate before the step of a) forming the bezel pattern. This is to selectively perform surface treatment according to the surface energy of the substrate in order to improve the coating properties of the ink and to remove stains caused by foreign substances.

Specifically, the surface treatment may be performed by treatment such as wet surface treatment, UV ozone, or atmospheric pressure plasma.

As a method of forming the bezel pattern on the substrate, a method selected from inkjet printing, gravure coating, and reverse offset coating using an ultraviolet curable resin may be used instead of photolithography and screen printing. In order to apply the above method, the viscosity of the ink composition of the present invention is preferably 1 to 20 mPa·s.

In order to form a bezel pattern on a specific part of the substrate by the above method, an ink composition having a low viscosity of 1 to 20 mPa·s is applied to a height of 0.1 to 20 μm, more specifically 0.5 to 5 μm. The applied composition is cured through exposure including ultraviolet rays, and as a result, a bezel pattern having a thin film thickness of 0.1 to 20 µm, more specifically 0.5 to 5 µm can be manufactured.

Light sources for curing the photopolymerizable composition for forming a bezel pattern of the present invention include, for example, mercury vapor arcs, carbon arcs, Xe arcs, and LED curing machines that emit light having a wavelength of 250 to 450 nm. It is not limited.

The optical density after curing the photopolymerizable composition for forming the bezel pattern is 0.1 to 1.5 based on the film thickness of 1.0 μm, and if necessary, may be 0.5 to 1.0. In this case, there is an advantage of excellent shielding characteristics by the bezel pattern. If the optical density exceeds 1.5, the required content of the pigment to be added is very high, so it may adversely affect the manufacture of ink and the inkjet process, and may inhibit the curing of the photopolymerizable composition for forming a bezel pattern by radiation. have.

The present invention provides a bezel pattern of a display substrate manufactured by the above method. In the present invention, the bezel pattern refers to a pattern formed on the edge of various devices such as a watch and a display device.

The optical density of the bezel pattern is 0.1 to 1.5 based on a film thickness of 1.0 μm, and may be 0.5 to 1.0 as necessary. In this case, there is an advantage of excellent shielding characteristics by the bezel pattern. If the optical density exceeds 1.5, the required content of the pigment to be added is very high, so it may adversely affect the manufacture of ink and the inkjet process, and may inhibit the curing of the photopolymerizable composition for forming a bezel pattern by radiation. have.

In addition, the present invention provides a display substrate including the bezel pattern.

The display includes a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD), and a thin film transistor liquid crystal. It may be used in any one of a display device (Thin Film Transistor-Liquid Crystal Display, LCD-TFT) and a cathode ray tube (CRT).

Hereinafter, the present invention will be described in detail by way of examples. The following examples are for explaining the present invention, and the scope of the present invention includes the ranges described in the following claims and their substitutions and modifications, and is not limited to the scope of the examples.

Example

After mixing in the composition shown in Table 1, the mixture was stirred for 24 hours to prepare a composition for forming a bezel pattern.

Pigment
Dispersion
(Pigment) Epoxy Oxetane Photoinitiator stick
Enhancer menstruum bookbinder Example A B C D E G H One 55 (13.75) 5 20 D1: 1 E1: 0.5 G1: 18.5 - 2 30(7.5) 15 35 D1: 3 E2: 0.5 G1: 10 H1: 6.5 3 15(3.75) 25 20 D2: 5 E1: 1 G2: 15 H2: 19 4 30(7.5) 8 32 D3: 5 E2: 3 G3: 10 H3: 12 5 5(1.25) 15 65 D4: 1 E1: 0.5 G4: 15 - 6 10(2.5) 15 55 D4: 1 E1: 0.5 G7: 10 H1: 10 7 20(5.0) 10 50 D4: 1 E1: 0.5 G8: 10 H1: 10 Comparative example One 30(7.5) 10 40 D1: 1 E2: 0.5 G5: 15 H3: 3.5 2 30(7.5) 10 34 D2: 5 E1: 1 G6: 10 H3: 10 3 30(7.5) 13 50 D5: 1 E2: 1 - H3: 5 4 30(7.5) 50 10 D6: 5 E1: 0.5 G6: 4.5 -

A1: Carbon black pigment dispersion (BK-5026, Tokushiki Corporation)

B: 3,4-epoxycyclohexylcarboxylate (TTA-21P, Tetrachem)

C: 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane (GASON DOX, Guarson Chemical)

D1: UVI-6992 (Dow company)

D2: UVI-6994 (Dow company)

D3: Irgacure 250 (BASF company)

D4: Omnicat 440 (IGM resin company)

D5: Rhodorsil 2074 (Rhodia company)

D6: CPI-100P (SAN-APRO company)

E1: KBM-303 (2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane, Shin-Etsu silicone)

E2: KBM-403 (3-glycidoxypropyl trimethoxysilane, synethsilicone)

G1: DEGBEA (Diethylene glycol monobutyl ether acetate, hereinafter BCA, boiling point 248℃)

G2: DEGEEA (Diethylene glycol monoethyl ether acetate, hereinafter ECA, boiling point 220°C)

G3: DEGDBE (diethylene glycol dibutyl ether, hereinafter BDGy, boiling point 250°C)

G4: DPMA (dipropylene glycol methyl ether acetate, boiling point 220°C)

G5: EGBE (ethylene glycol monobutyl ether, hereinafter BCs, boiling point 170℃)

G6: TPGBE (tripropylene glycol butyl ether, boiling point 291°C)

G7: Benzyl alcohol (boiling point 205℃)

G8: Diethylene glycol (boiling point 245℃)

H1: triethylene glycol divinyl ether, BASF

H2: 1,4-cyclohexanedimethanol divinyl ether, BASF

H3: isobutyl vinyl ether, BASF

<Production Example 1> Preparation of bezel pattern

The compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were coated on the cleaned LCD glass substrate by an inkjet coating method to a thickness of 2 μm after curing. In order to prevent adhesion of foreign substances, the bezel pattern was formed by curing the coating layer by irradiating ultraviolet rays under the following conditions within 1 minute after coating. The ultraviolet irradiator used a high-pressure mercury lamp, and was irradiated with a light amount of ^{1000mJ/cm 2 based on UV.}

<Production Example 2> Fabrication of a display device using a bezel pattern

A bezel pattern was formed on the upper surface of a display panel (hereinafter, referred to as panel) according to the method of Preparation Example 1, and an NRT polarizing film manufactured by LG Chem using an acrylic adhesive layer as an upper substrate was attached. After attaching, the surroundings were encapsulated with a sealant in order to prevent mixing of moisture and foreign matter into the gap between the polarizing film and the pattern.

Experimental example

<Experimental Example 1>: Viscosity

The viscosity was measured for the compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4. Brookfield's Viscometer DV-2 was used as a viscosity measuring device.

The measurement results are shown in Table 2 below, and when the viscosity of the composition is 20 mPa·s or less, the result is indicated by ○, and when the viscosity of the composition is 20 mPa·s or more, the result is indicated by X.

<Experimental Example 2>: Measurement of evaporation rate

Each composition was placed in a convection oven at a temperature of 35 degrees for a certain period of time, and the evaporation rate of the composition was observed. The definition of the evaporation rate was calculated as the ratio of the residue to the initial stage by putting each composition in an aluminum dish by 1 g by weight using a micro balance, and then measuring the weight of the composition remaining after the passage of time in a convection oven. The measurement results are shown in Table 2 below, and if the residual mass ratio is 85% or more after evaporation starts and after 2 hours have elapsed, it is indicated as ○, and if it is less than 85%, it is indicated as result X.

<Experimental Example 3>: Jetting stability

Each of the above compositions was continuously discharged for 1 minute using an experimental inkjet printer (UJ-200, Unijet), and then the discharge was stopped for 15 minutes so that the nozzles were dried by having a pause time, and then discharged again on the paper. Was carried out. It was evaluated whether the discharge of each composition was performed smoothly. The measurement results are shown in Table 2 below, and when the ink is normally discharged on the paper and a normal print is output, the result is indicated by ○, and when the quality of the print is degraded due to the occurrence of defective discharge due to drying of the ink, the result Is denoted by X.

<Experimental Example 4>: Curing sensitivity

Each of the compositions was coated on a glass substrate with a dropper, and spin coating was performed at a rotation speed of 1000 to 5000 rpm. Then, using a UV irradiation device (high pressure mercury lamp, Innocure 5000, Jeil UV), the composition was cured by irradiating ultraviolet rays with ^{a total exposure of 1000 mJ/cm 2.} The exposure amount was measured using a UV puck 2 (EIT) meter. The measurement results are shown in Table 2 below, and when touched after 1 minute after irradiation, when the liquid film is not completely cured and the liquid comes out, it is indicated by X. If the liquid film is not completely cured and stickiness remains, △, a thin film When it was completely cured and there was no stickiness, it was indicated by ○.

<Experimental Example 5>: Evaluation of the optical density/thickness of the bezel pattern

In the method of Preparation Example 1, the optical density/thickness of the composition coated to have a thickness of 1 μm on a general LCD glass substrate by spin coating instead of inkjet coating was measured using an OD measuring device manufactured by X-rite. The measured values are listed in Table 2.

Example Viscosity Evaporation rate Jetting stability Curing sensitivity Optical density/thickness One ○ ○ ○ ○ 1.03/1㎛ 2 ○ ○ ○ ○ 0.49/1㎛ 3 ○ ○ ○ ○ 0.26/1㎛ 4 ○ ○ ○ ○ 0.51/1㎛ 5 ○ ○ ○ ○ 0.11/1㎛ 6 ○ ○ ○ △ 0.19/1㎛ 7 ○ ○ ○ △ 0.33/1㎛ Comparative example One ○ X X ○ 0.50/1㎛ 2 ○ ○ ○ X - 3 X ○ ○ ○ 0.51/1㎛ 4 X ○ ○ ○ 0.50/1㎛

From the results of Table 1, in Examples 1 to 5 according to the present invention, a glycol alkyl ether solvent having a boiling point of 210°C to 260°C was used, and since the evaporation rate was low, the jetting stability was good, and the curing sensitivity was also good. Examples 6 to 7 used glycol and alcohol solvents having a boiling point of 190°C to 280°C, and the evaporation rate and jetting stability were good. Although the curing sensitivity was good, it was somewhat insufficient compared to Examples 1 to 5.

In contrast, in Comparative Example 1, since a glycol alkyl ether solvent having a boiling point of 170° C. was used, the evaporation rate was fast, and thus the jetting stability was poor.

In addition, since Comparative Example 2 used a glycol alkyl ether solvent having an excessively high boiling point of 291° C., since the evaporation rate was low, the jetting stability was good, but the curing rate was poor.

In addition, in the composition to which the solvent was not applied as in Comparative Example 3, the jetting stability was good because the boiling points of monomers such as ECC and DOX were 210° C. or higher, but the temperature was unnecessarily increased to lower the viscosity for the inkjet process due to high viscosity. Was necessary. In addition, since the content of the non-reactive volatile component in the liquid film was low, the thickness did not decrease even before/after curing, and the shading density/thickness was relatively insufficient.

However, since Comparative Example 4 contained 40% or more of the ECC composition, the viscosity was high even though the solvent was included, unlike Comparative Example 3, and thus the temperature was required to increase.

Claims (24)

coloring agent,
Epoxy monomer,
Oxetane monomer,
Photopolymerization initiator and
A solvent having a boiling point of 200 to 280°C, containing glycol-based ether,
The glycol-based ether is any one or more selected from the group consisting of diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, and dipropylene glycol methyl ether acetate. Formation photopolymerizable composition. The method according to claim 1,
A photopolymerizable composition for forming a bezel pattern, further comprising at least one selected from the group consisting of a surfactant, an adhesion enhancer, a diluent and a photosensitizer. The method according to claim 1,
The colorant is a photopolymerizable composition for forming a bezel pattern, characterized in that it contains at least one pigment and dye selected from the group consisting of carbon black, graphite, metal oxide, and organic black pigment. The method according to claim 1,
The content of the colorant is a photopolymerizable composition for forming a bezel pattern, characterized in that 1 to 15% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. The method according to claim 1,
The oxetane monomer is a photopolymerizable composition for forming a bezel pattern, comprising an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings. The method according to claim 1,
The content of the oxetane monomer is a photopolymerizable composition for forming a bezel pattern, characterized in that 20 to 70% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. The method according to claim 1,
The epoxy monomer is from the group consisting of a bisphenol-type epoxy monomer, a novolac-type epoxy monomer, a glycidyl ester-type epoxy monomer, a glycidyl amine-type epoxy monomer, a linear aliphatic epoxy monomer, a biphenyl-type epoxy monomer, and an alicyclic epoxy monomer. A photopolymerizable composition for forming a bezel pattern, characterized in that at least one selected. The method according to claim 1,
The content of the epoxy monomer is 5 to 40% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern, the photopolymerizable composition for forming a bezel pattern. The method according to claim 1,
The photopolymerization initiator is a photopolymerizable composition for forming a bezel pattern, characterized in that the iodonium salt or sulfonium salt. The method according to claim 1,
The photopolymerizable composition for forming a bezel pattern, characterized in that the content of the photopolymerization initiator is 0.5 to 10% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. delete delete delete delete The method according to claim 1,
The solvent is a photopolymerizable composition for forming a bezel pattern, characterized in that the boiling point is 200 ~ 260 ℃. The method according to claim 1,
The content of the solvent is a photopolymerizable composition for forming a bezel pattern, characterized in that 1 to 40% by weight based on the total weight of the photopolymerizable composition for forming the bezel pattern. The method according to claim 1,
The photopolymerizable composition for forming a bezel pattern, characterized in that the viscosity of the photopolymerizable composition for forming a bezel pattern is 1 to 20 mPa·s at 25°C. The method according to claim 1,
When the photopolymerizable composition for forming the bezel pattern is evaporated in a convection oven at 35° C., the remaining mass after 2 hours is 85% or more. a) forming a bezel pattern on a substrate by using the photopolymerizable composition for forming a bezel pattern of claim 1; And
b) A method of manufacturing a bezel pattern for a display substrate comprising the step of curing the bezel pattern. The method of claim 19,
The method of forming the bezel pattern on the substrate in step a) is a method selected from inkjet printing, gravure coating, and reverse offset coating. . The method of claim 19,
The method of manufacturing a bezel pattern for a display substrate, wherein the bezel pattern has a thickness of 0.1 μm to 20 μm. A bezel pattern for a display substrate formed on a substrate by curing the photopolymerizable composition for forming a bezel pattern of claim 1. The method of claim 22,
A bezel pattern for a display substrate, wherein an OD value of the bezel pattern is 0.1 to 1.5 per 1.0 μm of a film thickness. A display substrate comprising the bezel pattern for a display substrate of claim 22.

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