KR101835299B1 - Uv-curable ink composition, manufacturing method for bezel pattern of display panel and bezel pattern of display panel using the same - Google Patents

Abstract

An epoxy resin composition comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator and an adhesion promoter, wherein the epoxy resin: oxetane resin content ratio is 1: 0.5 to 1: 6, An ultraviolet ray curable ink composition of 4B or more in accordance with D3359 standard, a method of manufacturing a bezel pattern of a display substrate using the composition, and a bezel pattern using the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a UV-curable ink composition, a method of manufacturing a bezel pattern using the same,

The present invention relates to an ultraviolet curable ink composition, a method of manufacturing a bezel pattern of a display substrate using the composition, and a bezel pattern produced thereby.

In order to achieve weight reduction and thinning in a display device, a method of forming a bezel pattern on a substrate instead of using a separate bezel structure is used.

In the conventional method of forming a bezel pattern, a photosensitive resin composition based on free radical polymerization is used in most cases, but since the free radical polymerization resin composition has a large curing shrinkage, the bezel film may easily peel off from the substrate . Korean Patent Laid-Open Publication No. 2015-106665A discloses a colored photosensitive resin composition having excellent adhesion to a substrate including a adhesion promoter in order to solve such a problem. However, post-baking such as heating at a temperature of 200 degrees or more for 20 minutes, bake process is required.

Therefore, there is a need to develop a method of forming a bezel pattern that can easily improve adhesion to a substrate as compared with the conventional method of forming a bezel pattern.

KR 2013-0132322 A JP 5488175 B2 KR 2015-106665A

In order to solve the problems of the prior art, the present invention provides a method of manufacturing a bezel pattern using an ultraviolet curable ink composition having low shrinkage and adhesion to a glass base material when cured, a bezel pattern manufactured thereby, and a display And to provide a substrate.

In order to solve the above problems,

The present invention relates to a curable resin composition comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator, and a adhesion promoter, wherein the content ratio of the epoxy resin to the oxetane resin is 1: 0.5 to 1: 6, And an ultraviolet ray curable ink composition of 4B or more in accordance with ASTM D3359.

The present invention also provides a method of manufacturing a liquid crystal display, comprising: forming a bezel pattern on a substrate using the ultraviolet curable ink composition; And curing the bezel pattern. The present invention also provides a method for manufacturing a bezel pattern for a display substrate.

Further, the present invention provides a bezel pattern for a display substrate formed on a substrate by curing the ultraviolet curable ink composition.

The photosensitive resin composition according to one embodiment of the present invention can produce a bezel pattern having a higher adhesion to a glass substrate than a conventional bezel pattern.

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

The present invention relates to a curable resin composition comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator, and a adhesion promoter, wherein the content ratio of the epoxy resin to the oxetane resin is 1: 0.5 to 1: 6, And an ultraviolet ray curable ink composition of 4B or more in accordance with ASTM D3359.

The ultraviolet curable ink composition of the present invention may further comprise at least one selected from the group consisting of a surfactant, a diluent, and a photosensitizer.

In general, a radical polymerization type resin and a cationic polymerization type resin are mainly used in the ultraviolet curable ink composition. In the case of the radical polymerization type resin, since it is not suitable for the curing of the thin film due to the hardening trouble due to oxygen, and because the curing shrinkage is large, the adhesion to the glass substrate is low and it is not suitable for forming the bezel pattern. On the other hand, the cationic polymerization type resin is usually advantageous for curing the thin film since the curing shrinkage ratio is low and the influence by oxygen is small.

The ultraviolet curable ink composition used in the present invention includes an epoxy resin as a cationic curing component. The epoxy resin is preferably selected from among a bisphenol epoxy resin, a novolak epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic epoxy resin, a biphenyl type epoxy resin and an alicyclic epoxy compound Or a mixture of two or more of them.

The alicyclic epoxy compound may mean a compound containing at least one epoxidized aliphatic cyclic group.

In the above-mentioned cycloaliphatic epoxy compound containing an epoxidized aliphatic cyclic group, the epoxidized aliphatic cyclic group means an epoxy group bonded to an alicyclic ring, and examples thereof include 3,4-epoxycyclopentyl group, 3,4-epoxy (3,4-epoxycyclohexyl) ethyl group, a 3- (3,4-epoxycyclohexyl) ethyl group, an isopropylcyclopentylmethyl group, (3,4-epoxycyclopentyl) propyl group or 3- (3,4-epoxycyclohexyl) propyl group. The hydrogen atom constituting the alicyclic ring may optionally be substituted with a substituent such as an alkyl group. As the alicyclic epoxy compound, for example, a compound specifically exemplified below can be used, but epoxy compounds which can be used are not limited to the following types.

Vinylcyclohexene, vinylcyclohexene dioxide, limonene monoxide, limonene dioxide, (3,4-epoxycyclohexyl) methyl-cyclohexanecarboxylic acid, dicyclopentadiene oxide, cyclohexene oxide, (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis Epoxycyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexane (3,4-epoxycyclohexyl) ether, 3,4-epoxycyclohexene carboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Celllock 8000, < / RTI >

The content of the epoxy resin is preferably 5 to 60% by weight, more preferably 10 to 30% by weight based on the total weight of the ultraviolet curable ink composition. If it exceeds 60% by weight, the viscosity of the composition increases. If it is less than 5% by weight, the curing sensitivity is lowered.

The ultraviolet curable ink composition includes an oxetane resin as another cationic polymerizable monomer.

The oxetane resin is a compound having a quaternary cyclic ether group in its molecular structure and can act to lower the viscosity of the cationically cured ink composition (for example, less than 50 cPs at 25 캜).

Specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-cyclohexyloxymethyloxetane or Phenol novolak oxetane, and the like. Examples of the oxetane compound include "Alon oxetane OXT-101", "Alon oxetane OXT-121", "Alon oxetane OXT-211", "Alon oxetane OXT-221" &Quot; Alon oxetane OXT-212 " and the like can be used. These may be used alone or in combination of two or more.

The content of the oxetane resin is preferably 15 to 80% by weight, more preferably 40 to 60% by weight based on the total weight of the ultraviolet curable ink composition. If it is more than 80% by weight, the curing sensitivity is low, and if it is less than 15% by weight, the viscosity increases and coating properties are deteriorated.

The oxetane resin of the present invention can be used in combination with 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 oxetane compounds are used together as described above, the content range of the oxetane compound having one oxetane ring: the oxetane compound having two oxetane rings is in the range of 1:16 to 1: 3 Is preferably used.

Further, the present invention is characterized in that the content ratio of the epoxy resin: oxetane resin is 1: 0.5 to 1: 6. When the ratio of the epoxy compound to the oxetane compound is more than 1: 6, the viscosity of the composition is low and the coating property of the composition is excellent, but the curing sensitivity may be lowered. When the ratio is less than 1: 0.5, The coating properties may be deteriorated.

The ink composition of the present invention is a cationic photopolymerization initiator which contains a compound capable of forming a cationic species or a Bronsted acid by irradiation with ultraviolet rays, for example, an iodonium salt or a sulfonium salt. However, It is not.

The iodonium salt or the sulfonium salt causes a curing reaction to form a polymer by reacting monomers having an unsaturated double bond contained in the ink during the ultraviolet curing process, and a photosensitizer may be used depending on the polymerization efficiency.

For example, the photopolymerization initiator may have an anion represented by SbF ₆ -, AsF ₆ -, BF ₆ -, (C ₆ F ₅ ) ₄ B-, PF ₆ - or RfnF _{6 -n} , It is not.

The photopolymerization initiator is preferably contained in an amount of 1 to 15% by weight, more preferably 2 to 10% by weight based on the total weight of the UV curable ink composition. When the content of the photopolymerization initiator is less than 1% by weight, the curing reaction is not sufficient. When the content of the photopolymerization initiator is more than 15% by weight, the photopolymerization initiator is not dissolved or the viscosity is increased.

The ultraviolet curable ink composition may further include an adhesion promoter as an additive.

The film attached on the bezel pattern is repeatedly subjected to shrinkage and expansion depending on conditions of use such as temperature and humidity, so that the bezel pattern is stressed, and the film and the bezel may be separated from the glass substrate. In order to prevent this, as adhesion promoting agents, 1 (meth) acryloyl group-containing compounds selected from the group consisting of amino silane compounds, alkoxysilane compounds, epoxy silane compounds, aminophenyl silane compounds, aminosilane compounds, mercapto silane compounds and vinyl silane compounds Excellent results can be obtained when a silane-based compound of a species or more is used.

Among them, an epoxy silane compound is more preferable as the adhesion promoter of the present invention.

In one embodiment of the present invention, an epoxy silane compound was used as the adhesion promoter, and excellent adhesion was observed between the bezel pattern and the glass substrate. Specifically, the adhesion of the ultraviolet-curable ink composition of the present invention to the glass substrate after curing may be 4B or more in accordance with ASTM D3359.

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, the bezel pattern can not be prevented from being peeled off from the glass substrate. If it exceeds 15% by weight, the viscosity of the ink solution increases and the dispersibility is low.

The ink composition may further include a diluent to improve the coating property by lowering the viscosity of the ink to increase the flowability.

Examples of the diluent include methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol di But are not limited to, ethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxypropanol, 2-methoxypropanol, 2-ethoxyethanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, From the group consisting of ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, dipropylene glycol monomethyl ether, cyclohexene oxide and propylene carbonate One or more selected species may be used, But is not limited thereto.

The content of the diluent is preferably 0 to 30% by weight, more preferably 0.1 to 20% by weight based on the total weight of the UV curable ink composition. If it is more than 30% by weight, the curing sensitivity is lowered.

The ultraviolet curable ink composition includes a colorant.

As the coloring agent, one or more kinds of pigments, dyes, or a mixture thereof can be used, and there is no particular limitation so long as it can express colors as required.

As one specific example of the present invention, carbon black, graphite, metal oxide, organic black pigment and the like can be used as a black pigment.

Examples of carbon blacks are cysteine 5HIISAF-HS, cysto KH, cysteo 3HHAF-HS, cysteo NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, , SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTO 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, # 25, # 45, # 45, # 45, # 45, # 45, # 25, # CF9, # 95, # 20, # 2300, # 2350, # 2300, # 2200, # 1000, # 980, # 900, 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical); PRINTEX-25, PRINTEX-25, PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, 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; 890, RAVEN-880ULTRA, RAVEN-880ULTRA, RAVEN-850R, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1040ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN- RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (Colombia Carbon) or mixtures thereof.

Examples of the organic black pigment include aniline black, lactam black, perylene black, and the like, but the present invention is not limited thereto.

In the present invention, the ultraviolet curable ink composition is cured by irradiation with ultraviolet light (e.g., 250 or 450 nm), more preferably ultraviolet light with a long wavelength (e.g., 360 to 410 nm) to have a certain level of OD . For this purpose, 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 ultraviolet curable ink composition. When the content of the colorant is less than 1% by weight, a level of OD that can be applied to the bezel is not exhibited. When the content is more than 15% by weight, 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 can be maintained in the range of 0.05 to 2.5 per 1.0 탆 of the film thickness.

The ultraviolet curable ink composition includes a surfactant that lowers the surface tension of the ink composition to exhibit a small taper angle.

Examples of the surfactant include commercially available products such as Megafack F-444, F-475, F-478, F-479, F-484, F-550 and F-552 manufactured by Dai Nippon Ink & Surflon S-111, S-112, S-113, S-121, S-131, S-132 and S-141 of Asahi Glass Co., Ltd. and F-553, F-555, F- S-145 or Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 from Sumitomo 3M, Zonyl FS- BYK-306, BYK-310, BYK-310 and BYK-306 of BYK-FSN-100 and FSO and BYK-BYK-310, BYK-320, BYK-330, BYK-331, BYK- BYK-380, BYK-398, BYK-398, BYK-398, BYK-398, BYK- In the group consisting of BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, BYK-SILCLEAN 3700 and BYK-UV 3570 or Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370 and Flow 425 You can use what is selected.

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 UV curable ink composition. When the content of the surfactant is less than 0.1% by weight, the effect of lowering the surface tension of the composition is insufficient, resulting in coating failure when the composition is coated on the substrate. When the content exceeds 5.0% by weight, There is a problem that the compatibility and the defoaming property of the composition are rather reduced.

The ultraviolet curable ink composition may further include a photosensitizer to compensate the curing property of the long wavelength active energy ray.

The photosensitizer may be an anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxy

Anthracene-based 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- Benzophenone-based compounds such as dimethyl-4-methoxybenzophenone and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Acetophenone; Ketone-based compounds such as dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and propanone; Perylene; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, isopropylthioxanthone (ITX), diisopropylthioxanthone, 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-acridinylpentane), 1,3-bis (9-acridinyl) propane, and the like 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-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Benzoate-based compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis Amino-synergists such as methyl-cyclopentanone; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- -Benzoyl-7-methoxy-coumarin, 10,10-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- Pyran o [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene; And 3-methyl-b-naphthothiazoline.

The photosensitizer is preferably contained in an amount of 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the photopolymerization initiator. If the amount is less than 1 part by weight, the curing sensitivity can not be enhanced at a desired wavelength. If the amount exceeds 200 parts by weight, the photosensitizer may not be dissolved and the pattern adhesion and crosslinking density may be lowered.

The ultraviolet curable ink composition used in the present invention spreads within a short time immediately after inkjet printing, exhibits excellent coating film characteristics, and exhibits excellent adhesion properties by curing. Therefore, it is preferable that the UV-lamp is installed immediately after the ink-jet head so that the UV-curable ink composition can be cured simultaneously with the ink-jet printing.

The ultraviolet curable ink composition has a curing dose of 1 to 10,000 mJ / cm 2, preferably 80 to 2,000 mJ / cm 2.

The ultraviolet curable ink composition is cured by absorbing radiation in a wavelength range of 250 nm to 450 nm, preferably 360 nm to 410 nm.

The ultraviolet curable ink composition is suitable for inkjet processing, for example, by having a viscosity of 1 cP to 50 cP at 25 캜, more preferably 3 cp to 45 cp at 25 캜. The ultraviolet curable ink composition having the viscosity range described above has good ejection at the process temperature. The process temperature means a temperature at which the viscosity of the curable ink composition is lowered. The process temperature may be from 10 캜 to 100 캜, and preferably from 20 캜 to 70 캜.

The ultraviolet ray hardening type ink composition contains adhesion promoting agent, so that the adhesiveness to the glass substrate of the bezel pattern formed according to the present invention is 4B or more in accordance with ASTM D3359 standard, and is excellent in adhesion and coating property.

The method of manufacturing the bezel pattern of the display substrate of the present invention uses the ultraviolet curable ink composition.

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

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

Specifically, the surface treatment may be carried out by a treatment such as a wet surface treatment, UV ozone, atmospheric plasma or the like.

As a method of forming a bezel pattern on the substrate, a method selected from inkjet printing, gravure coating and reverse offset coating using an ultraviolet ray hardening resin instead of photolithography and screen printing may be used. In order to apply the above method, the viscosity of the ink composition of the present invention may be 1 cP to 50 cP, preferably 3 cp to 45 cp.

The ink composition having a low viscosity of 1 cP to 50 cP is applied at a height of 0.1 to 20 탆, more specifically 0.5 to 5 탆, in order to form a bezel pattern on a specific part of the substrate by the above method. The applied composition is cured through exposure to light including ultraviolet rays, so that a bezel pattern having a thin film thickness of 0.1 to 20 mu m, more specifically 0.5 to 5 mu m, can be produced.

Examples of the light source for curing the ultraviolet ray curable ink composition according to the present invention include mercury vapor arc, carbon arc, Xe arc, LED curing light, and the like which emit light having a wavelength of 250 to 450 nm, Do not.

The bezel pattern is characterized in that the taper angle measured after curing treatment is more than 0 DEG and 30 DEG and the thickness is 0.1 mu m to 20 mu m. Further, the taper angle may preferably be more than 0 [deg.] And 10 [deg.]. Further, the thickness may preferably be 0.5 탆 to 5 탆. The bezel pattern of the present invention may not exhibit short-circuiting due to a large step, bubble generation, and deterioration of visual quality due to film release.

The optical density of the bezel pattern may be 0.05 to 2.5, preferably 0.25 to 1.0, per 1.0 탆 of the film thickness. In this case, there is an advantage that the shielding property by the bezel pattern is excellent. If the optical density exceeds 2.5, the required content of the pigment to be added becomes extremely high, which may adversely affect the ink production and inkjet process, and may hinder the ultraviolet curable ink composition from being cured by radiation.

The bezel pattern has adhesion to the glass substrate after curing treatment of 4B or more in accordance with ASTM D3359, and is excellent in adhesion and coating properties.

The present invention provides a bezel pattern of a display substrate manufactured by the above method. In the present invention, a bezel pattern refers to a pattern formed at the edges of various devices such as a clock, a display device, and the like.

The bezel pattern is characterized in that the taper angle measured after curing treatment is more than 0 DEG and 30 DEG and the thickness is 0.1 mu m to 20 mu m. Further, the taper angle may preferably be more than 0 [deg.] And 10 [deg.]. Further, the thickness may preferably be 0.5 탆 to 5 탆. The bezel pattern of the present invention may not exhibit short-circuiting due to a large step, bubble generation, and deterioration of visual quality due to film release.

The optical density of the bezel pattern may be 0.05 to 2.5, preferably 0.25 to 1.0, per 1.0 탆 of the film thickness. In this case, there is an advantage that the shielding property by the bezel pattern is excellent. If the optical density exceeds 2.5, the required content of the pigment to be added becomes extremely high, which may adversely affect the ink production and inkjet process, and may hinder the ultraviolet curable ink composition from being cured by radiation.

The bezel pattern has adhesion to the glass substrate after curing treatment of 4B or more in accordance with ASTM D3359, and is excellent in adhesion and coating properties.

The present invention also provides a display substrate including the bezel pattern.

The display may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD) A cathode ray tube (CRT), a cathode ray tube (CRT), a display device (Thin Film Transistor-Liquid Crystal Display), and the like.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples illustrate the present invention and the scope of the present invention includes the scope of the following claims and substitutions and modifications thereof, which are not intended to limit the scope of the embodiments.

<Examples>

And the mixture was stirred for 3 hours to prepare compositions for forming the bezel patterns of Examples 1 to 9 and Comparative Examples 1 to 3.

coloring agent Epoxy Oxetane polymerization
Initiator Interface
Activator stick
Enhancer Example A B C D E F One A1: 5 B1: 20 C2: 68 D1: 4 E1: 1 F1: 2 2 A1: 5 B2: 30 C2: 58 D1: 4 E1: 1 F2: 2 3 A1: 5 B2: 30 C2: 58 D2: 4 E1: 1 F3: 2 4 A1: 5 B1: 30 C1: 15
C2: 43 D3: 4 E1: 1 F4: 2 5 A1: 5 B1: 30 C1: 15
C2: 43 D4: 4 E1: 1 F5: 2 6 A1: 5 B1: 30 C3: 15
C2: 43 D5: 4 E1: 1 F6: 2 7 A1: 5 B1: 20 C2: 62 D4: 4 E1: 1 F1: 8 8 A1: 5 B2: 30 C2: 52 D4: 4 E1: 1 F2: 8 9 A1: 5 B2: 30 C1: 15
C2: 37 D4: 4 E1: 1 F3: 8 Comparative Example One A1: 5 B1: 30 C2: 59 D1: 5 E1: 1 - 2 A1: 5 B2: 30 C2: 59 D1: 5 E1: 1 - 3 A1: 5 B2: 30 C2: 39 D2: 5 E1: 1 F1: 20

A1: carbon black

B1: Celllock 2021P (Daicel Corporation)

B2: Celllock 3000 (manufactured by Daicel Corporation)

C1: Aron oxetane 101 (Toagosei)

C2: Aron oxetane 221 (Toagosei)

C3: Aron oxetane 212 (Toagosei)

C4: Aron oxetane 121 (Toagosei)

D1: CPI-200K (San-Afro)

D2: Irgacure 270 (BASF)

D3: Irgacure 290 (BASF)

D4: UV-694 (tetrachem)

D5: Rhodorsil 2074 (Blue star silicone)

E1: BYK-330 (BYK chemie)

F1: KBM-303 (Shin-Etsu)

F2: KBE-402 (Shin-Etsu)

F3: KBM-403 (Shin-Etsu)

F4: KBE-403 (Shin-Etsu)

F5: KBM-503 (Shin-Etsu)

F6: KBE-503 (Shin-Etsu))

&Lt; Preparation Example 1 > Preparation of bezel pattern

The compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were cured on a cleaned LCD glass substrate and then coated by an ink-jet coating method so as to have a thickness of 2 mu m. The coating layer was irradiated with ultraviolet rays under the following conditions and cured to form a bezel pattern within 1 minute after coating in order to prevent adhesion of foreign matter. The ultraviolet irradiator used was a high pressure mercury lamp and irradiated with a light quantity of 1000 mJ / cm ² based on UVV.

Production Example 2 Production of Display Device Using Bezel Pattern

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

Experimental Example 1: Viscosity

The viscosities of the compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were measured. Brookfield's DV- + was used as a viscosity measuring instrument.

&Lt; Experimental Example 2 >: Measurement of curing sensitivity

In order to measure the curing sensitivity of the bezel pattern prepared according to Preparation Example 1, the state of the surface was confirmed by pressing the latex glove after 5 minutes passed after the ultraviolet irradiation.

○: The bezel pattern is not sticky, and is fully cured.

△: Bezel pattern hardened but sticky

X: Insufficient curing of the bezel pattern caused unreacted residues

Experimental Example 3: Bezel pattern OD evaluation

The OD of the composition coated on a general LCD glass substrate to a thickness of 1 mu m by spin coating instead of the ink-jet coating in the method of Production Example 1 was measured using an X-rite OD measuring machine.

&Lt; Experimental Example 4 >: Cross-hatch adhesion force

The cross-cut test was performed on the bezel pattern prepared in Production Example 1 in accordance with the standard of ASTM D3359, which is a crosscut test standard. The heat treatment may be performed for one minute at a temperature of 60 degrees to promote the reaction of the adhesion promoter according to the sample before performing the crosscut test. Specifically, the specimens were cut into 11 squares in the horizontal and vertical directions at intervals of 1 mm, and 100 square squares with 1 mm width and 1 mm squared were formed. Thereafter, when the CT-24 adhesive tape of Nichiban Co., Ltd. was attached to the cutting surface and then removed, the state of the falling surface was measured and evaluated based on the following criteria.

&Lt; Cross-hatch adhesion evaluation standard >

5B: When there is no falling side

4B: If the distance between the sides is less than 5% of the total area

3B: When the distance from the surface is 5 to 15% of the total area

2B: When the distance from the surface is 15 to 35% of the total area

1B: When the distance from the surface is 35 to 65% of the total area

0B: Almost all fall

Example Viscosity Whether or not hardened Lower adhesion Condition (cP) After 5 minutes of UV irradiation,
○: tack-free
Δ: tackiness
X: unreacted ASTM-D3359 One 25 ○ 4B 2 15 ○ 5B 3 15 ○ 5B 4 30 ○ 5B 5 31 ○ 4B 6 30 ○ 4B 7 22 ○ 5B 8 14 ○ 5B 9 15 ○ 5B Comparative Example One 120 ○ 0B 2 45 ○ 0B 3 35 × With poor curing
Not measurable

Referring to Table 2, it can be seen that the bezel patterns produced using the ink compositions of Examples 1 to 9 exhibit curing sensitivity similar to those of the comparative examples, and that the adhesiveness to the glass substrate is generally superior to the comparative examples .

Claims (31)

An ultraviolet curable ink composition comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator, a surfactant, and an adhesion promoter,
The weight ratio of the epoxy resin to the oxetane resin is 1: 1.73 to 1: 6,
Wherein the adhesion promoter is an epoxy silane compound,
The content of the adhesion promoter is 2 to 8% by weight based on the total weight of the ultraviolet-curable ink composition,
The adhesive force to the glass substrate after curing is 4B or more in accordance with ASTM D3359,
Wherein a taper angle of the ultraviolet-curable ink composition after curing is 0 占 to 10 占 The ultraviolet-curable ink composition for forming a bezel pattern of a display substrate. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, further comprising at least one selected from the group consisting of a diluent and a photosensitizer. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the oxetane resin comprises an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings . 4. The method according to claim 3, wherein the weight ratio of the oxetane compound having one oxetane ring: oxetane compound having two oxetane rings is 1: 16 to 1: 3. And an ultraviolet ray curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the content of the epoxy resin is 5 to 60% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the content of the oxetane resin is 15 to 80% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the photopolymerization initiator is an iodonium salt or a sulfonium salt. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the content of the photopolymerization initiator is 1 to 15% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the content of the colorant is 1 to 15% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 2, wherein the content of the diluent is 0 to 30% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the surfactant is a fluorine-based surfactant. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the surfactant is contained in an amount of 0.1 to 5.0% by weight based on the total weight of the ultraviolet curable ink composition. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 2, wherein the photosensitizer is contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of the photopolymerization initiator. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the ultraviolet curable ink composition has a curing dose of 1 to 10,000 mJ / cm 2. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 1, wherein the viscosity of the ultraviolet curable ink composition is 1 cp to 50 cp at 25 캜. The UV curable ink composition for forming a bezel pattern of a display substrate according to claim 15, wherein the viscosity of the ultraviolet curable ink composition is 3 cp to 45 cp at 25 캜. a) forming a bezel pattern on a substrate using the ultraviolet curable ink composition of claim 1; And
b) curing the bezel pattern, the method comprising the steps of:
Wherein the bezel pattern has a taper angle of 0 DEG to 10 DEG. 18. The method of claim 17, further comprising cleaning and drying the substrate prior to forming the bezel pattern. The method for manufacturing a bezel pattern for a display substrate according to claim 18, wherein the step of cleaning and drying the substrate is carried out by one or more treatments selected from the group consisting of wet surface treatment, UV ozone treatment and atmospheric pressure plasma treatment . [17] The method of claim 17, wherein 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. A method of manufacturing a bezel pattern. [19] The method of claim 17, wherein the step a) is performed at a processing temperature of 10 [deg.] C to 100 [deg.] C. [22] The method of claim 21, wherein the step a) is performed at a process temperature of 20 [deg.] C to 70 [deg.] C. [19] The method of claim 17, wherein the thickness of the bezel pattern is 0.1 [mu] m to 20 [mu] m. 26. The method of claim 23, wherein the thickness of the bezel pattern ranges from 0.5 [mu] m to 5 [mu] m. [Claim 17] The method of claim 17, wherein the OD value of the bezel pattern is 0.05 to 2.5 per 1.0 [micro] m thickness. [Claim 17] The method according to claim 17, wherein the adhesion of the bezel pattern to the glass base material is 4B or more in accordance with ASTM D3359. A bezel pattern for a display substrate formed on a substrate by curing the ultraviolet-curable ink composition of claim 1, wherein the bezel pattern has a taper angle of 0 ° to 10 °. [27] The bezel pattern for a display substrate according to claim 27, wherein the thickness of the bezel pattern is 0.1 [mu] m to 20 [mu] m. 27. The bezel pattern for a display substrate according to claim 28, wherein the thickness of the bezel pattern is 0.5 mu m to 5 mu m. 27. The bezel pattern for a display substrate according to claim 27, wherein an OD value of the bezel pattern is 0.05 to 2.5 per 1.0 mu m in film thickness. 27. The bezel pattern for a display substrate according to claim 27, wherein the adhesion of the bezel pattern to the glass substrate is 4B or more in accordance with ASTM D3359.