WO2016048115A1

WO2016048115A1 - Uv-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby

Info

Publication number: WO2016048115A1
Application number: PCT/KR2015/010341
Authority: WO
Inventors: 박성은; 구용성; 백승아; 김준형
Original assignee: 주식회사 엘지화학
Priority date: 2014-09-26
Filing date: 2015-09-30
Publication date: 2016-03-31

Abstract

The present invention relates to a UV-curable ink composition, a method for producing a bezel pattern of a display substrate using same, and a bezel pattern produced thereby, the UV-curable ink composition comprising a colorant, an epoxy resin, an oxetane resin, and a photopolymerization initiator, wherein the content ratio of the epoxy resin to the oxetane resin is 1:0.5-1:6.

Description

UV curable ink composition, method for manufacturing bezel pattern of display substrate using same and bezel pattern manufactured thereby

This application is filed with Korean Patent Application No. 10-2014-0129417 filed on September 26, 2014, Korean Patent Application No. 10-2014-0178523 filed on December 11, 2014, and Korean Patent Application No. 10-2015 filed on September 30, 2015. Claiming the benefit of priority based on -0138094, all contents disclosed in the literature of the relevant Korean patent application are incorporated as part of this specification.

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

In recent years, in order to achieve weight reduction and thinning, display apparatuses have used a method of directly printing a bezel-shaped light shielding pattern on a substrate instead of using a separate bezel structure.

Korean Patent Registration No. 10-1391225 discloses a technique for forming a bezel pattern using a photosensitive resin composition. However, conventional photosensitive resin compositions for forming bezel patterns contain a large amount of diluents in order to dilute the high viscosity, and thus there is a problem that a pre-bake process is required at a high temperature before exposure. Furthermore, in the conventional method of manufacturing a display substrate, a photolithography method or a screen printing method is used to form a bezel pattern. However, in the case of the photolithography method, a manufacturing cost for forming a pattern is expensive and the process is complicated. In the case of the screen printing method, there is a problem that a step between the bezel layer and the substrate occurs because the thickness of the pattern formed due to the high viscosity of the composition is high as several tens of micrometers.

Accordingly, there is a need to develop a material for forming bezel pattern having sufficient light shielding characteristics while having a thin thickness and a soft taper as compared to the conventional bezel pattern forming method.

In order to solve the above problems of the prior art, the present invention does not include a diluent or has a low viscosity despite containing a small amount, the ultraviolet light that can provide a bezel of a small taper angle and a thin film thickness when forming a bezel pattern It is an object to provide a curable ink composition.

In order to solve the above problems,

This invention provides a ultraviolet curable ink composition which contains a coloring agent, an epoxy resin, an oxetane resin, and a photoinitiator, and whose content ratio of the said epoxy resin: oxetane resin is 1: 0.5-1: 6.

In another aspect, the present invention, using the ultraviolet curable ink composition, forming a bezel pattern on a substrate; And hardening the bezel pattern; provides a method of manufacturing a bezel pattern for a display substrate comprising a.

Moreover, this invention provides the bezel pattern for display substrates which the said ultraviolet curable ink composition hardened | cured and formed on the board | substrate.

According to the present invention, a bezel pattern is formed by using an ultraviolet curable ink composition which exhibits a small taper angle and a thin film thickness when cured. Thus, a bezel pattern that does not exhibit deterioration of visibility due to short circuits due to large steps, bubble generation, and mold release. Can be prepared.

The bezel pattern manufacturing method of the present invention can be prepared without the high temperature process by using a UV curable ink composition having a low viscosity and excellent curing sensitivity, even if it does not contain a diluent or contains a small amount.

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

In addition, the ultraviolet curable ink composition of the present invention may further include any one or more selected from the group consisting of surfactants, adhesion promoters, diluents and photosensitizers.

Typically, a radically polymerizable resin and a cationic polymerizable resin may be mainly used in the ultraviolet curable ink composition. The radically polymerizable resin is not suitable for curing the thin film because it is impaired in curing due to oxygen, and is not suitable for bezel pattern formation due to its low adhesion to the glass substrate because of its large shrinkage. On the other hand, in the case of cationic polymerization type resin, it is generally advantageous to cure the thin film because the curing shrinkage rate is low and the influence by oxygen is small.

The ultraviolet curable ink composition used by this invention contains an epoxy resin as a cationic curing component. Specifically, the epoxy resin is selected from a bisphenol type epoxy resin, a novolak type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a linear aliphatic epoxy resin, a biphenyl type epoxy resin, and an alicyclic epoxy compound. It may be one kind or a mixture of two kinds.

The alicyclic epoxy compound may mean a compound including at least one epoxidized aliphatic ring group.

In the alicyclic epoxy compound containing an epoxidized aliphatic ring group, the epoxidized aliphatic ring group means an epoxy group bonded to an alicyclic ring, for example, a 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- epoxycyclo petyl) propyl group or 3- (3, 4- epoxy cyclohexyl) propyl group, can be illustrated. The hydrogen atom constituting the alicyclic ring in the above may be optionally substituted with a substituent such as an alkyl group. As said alicyclic epoxy compound, although the compound specifically illustrated below can be used, the epoxy compound which can 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-epoxycyclohexene carboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, dicel corporation Celoxide 8000 etc. can be used.

The content of the epoxy resin is preferably 5 to 60% by weight, and more preferably 10 to 30% by weight based on the total weight of the ultraviolet curable ink composition. When it exceeds 60 weight%, the viscosity of a composition will rise, and when it is less than 5 weight%, hardening sensitivity will fall.

The ultraviolet curable ink composition contains an oxetane resin as another cationically polymerizable monomer.

The oxetane resin is a compound having a four-membered cyclic ether group in its molecular structure, and can act 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 can be exemplified. As an oxetane compound, For example, "Alon oxetane OXT-101", "Alon oxetane OXT-121", "Alon oxetane OXT-211", "Alon oxetane OXT-221" of Toagosei Co., Ltd., or "Alonoxetane OXT-212" etc. can be used. These can be used individually or in combination of 2 or more types.

The content of the oxetane resin is preferably 15 to 80% by weight, and more preferably 40 to 60% by weight based on the total weight of the ultraviolet curable ink composition. When it exceeds 80 weight%, hardening sensitivity is low, and when it is less than 15 weight%, a viscosity will rise and coating property will fall.

In addition, the oxetane resin of this invention can be used including the oxetane compound which has one oxetane ring, and the oxetane compound which has 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 the flexibility of the membrane can be adjusted. When two kinds 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.

In addition, 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 and the oxetane compound exceeds 1: 6, the coating composition of the composition may be excellent due to the low viscosity of the composition, but the curing sensitivity may be lowered. When the ratio is less than 1: 0.5, the viscosity of the composition may be high. Therefore, the coating property may be lowered.

The ink composition of the present invention includes, as a cationic photopolymerization initiator, a compound which produces a cation species or bronsted acid by irradiation of ultraviolet rays, for example, an iodonium salt or a sulfonium salt, but is not limited thereto. It doesn't happen.

The iodonium salt or sulfonium salt may cause a curing reaction to form a polymer by reacting monomers having unsaturated double bonds contained in the ink during UV curing, and may use a photosensitizer according to 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 , but is not limited thereto. It is not.

The photopolymerization initiator is preferably included in 1 to 15% by weight, more preferably 2 to 10% by weight based on the total weight of the ultraviolet curable ink composition. If the content of the photopolymerization initiator is less than 1% by weight, the curing reaction may not be sufficient. If the content of the photopolymerization initiator is more than 15% by weight, all of the photopolymerization initiator may not be dissolved or the viscosity may increase, thereby decreasing the coating property.

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

The diluent includes 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 Ethyl ether, diethylene glycol methyl ethyl ether, 2-ethoxy propanol, 2-methoxy propanol, 2-ethoxy ethanol, 3-methoxy butanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol 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 You can use one or more selected It is not limited to this.

The content of the diluent is preferably 0 to 30% by weight, and more preferably 0.1 to 20% by weight, based on the total weight of the ultraviolet curable ink composition. If it is more than 30 weight%, hardening sensitivity will fall.

The ultraviolet curable ink composition includes a colorant.

As the colorant, one or more pigments, dyes or mixtures thereof can be used, and any color can be expressed as long as the color can be expressed as necessary.

As one specific example of the present invention, carbon black, graphite, metal oxides, organic black pigments or the like can be used as the black 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 , 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, # 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, RAVEN-1170 (Colombia Carbon, Inc.), or mixtures thereof.

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

In the present invention, the ultraviolet curable ink composition is cured by irradiation of ultraviolet light (for example, 250 or 450 nm), more preferably long wavelength ultraviolet light (for example, 360 nm to 410 nm) to have a certain level of optical density (OD). It features. To this end, the content of the colorant is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight based on the total weight of the ultraviolet curable ink composition. If the content of the colorant is less than 1% by weight, there is no level of OD applicable to the bezel, and if it is more than 15% by weight, the excess colorant is not 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 0.05 to 2.5 per 1.0 μm 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.

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 DaiNippon Ink & Chemicals Co., Ltd. Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141 and F-553, F-555, F-570, RS-75 or Asahi Glass 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 Zonyl FS-300, FSN from Dupont, BYK-306, BYK-310, BYK-320, BYK-330, 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 You can use what is selected.

The surfactant is preferably included in 0.1 to 5.0% by weight, more preferably 0.5 to 3.0% by weight relative to the total weight of the ultraviolet 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 not sufficient, so coating defects occur when the composition is coated on the substrate. When the content of the surfactant exceeds 5.0% by weight, the surfactant is used in an excessive amount. There is a problem that the compatibility and anti-foaming of the composition is rather reduced.

The ultraviolet curable ink composition may further include a photosensitizer to compensate for the sclerosis in the long wavelength active energy ray.

The photosensitizer includes anthracene-based compounds such as anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 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 dimethoxy acetophenone, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and propanone; Perylene; Fluorenone compounds such as 9-florenone, 2-chloro-9-prorenone, and 2-methyl-9-florenone; Such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone (ITX) and diisopropyl thioxanthone Thioxanthone type 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 Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, 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-based compounds such as pyrano [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylamino chalcone and 4-azidebenzalacetophenone; 2-benzoylmethylene; And 3-methyl-b-naphthothiazoline may be one or more selected from the group consisting of.

The photosensitizer is preferably included 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 less than 1 part by weight can not be expected to increase the curing sensitivity at the desired wavelength, if more than 200 parts by weight there is a problem in that the photosensitizer is not dissolved and the adhesion and crosslinking density of the pattern is reduced.

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

The film attached to the bezel pattern is repeatedly contracted and expanded according to the use conditions such as temperature and humidity, so that the bezel pattern is stressed so that the film and the bezel may be removed from the glass substrate. In order to prevent this, at least one silane compound selected from the group consisting of an alkoxy silane compound, an epoxy silane compound, an aminophenyl silane compound, an amino silane compound, a mercapto silane compound and a vinyl silane compound is used as an adhesion promoter. When used, excellent results can be obtained.

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

The adhesion promoter is preferably included in 0.1 to 15% by weight based on the total weight of the ink composition, more preferably 2 to 10% by weight. If the amount is less than 0.1 wt%, the bezel pattern may not be prevented from being peeled from the glass substrate. If the amount is more than 15 wt%, the viscosity of the ink solution may be increased and the dispersibility may be low.

The ultraviolet curable ink composition used in the present invention spreads within a short time immediately after inkjet printing, exhibits excellent coating film properties, and cures to exhibit excellent adhesive properties. Therefore, when applying the UV-curable ink composition, it is preferable to install a UV-lamp immediately behind the inkjet head so that the inkjet printing can be cured at the same time.

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 the wavelength range of 250 nm to 450 nm, preferably 360 nm to 410 nm.

The UV curable ink composition is, for example, suitable for an inkjet process by having a viscosity of 1 cP to 50 cP at 25 ° C., more preferably 3 cps to 45 cps or less at 25 ° C. The ultraviolet curable ink composition having the above viscosity range has a good discharge at the process temperature. The said process temperature means the temperature heated so that the viscosity of a curable ink composition may become low. The process temperature may be 10 ° C to 100 ° C, preferably 20 ° C to 70 ° C.

The ultraviolet curable ink composition is excellent in adhesion and coating property to the glass substrate.

In addition, the bezel pattern formed according to the present invention with the ultraviolet curable ink composition is excellent in adhesion to the upper substrate.

The upper end of the bezel pattern formed of the ultraviolet curable ink composition is attached to the upper substrate via an adhesive layer for the upper substrate, wherein the ultraviolet curable ink composition is an acrylic adhesive, a styrene butadiene rubber adhesive, an epoxy adhesive, a polyvinyl alcohol adhesive, Since the adhesive for the upper base material such as a polyurethane-based pressure-sensitive adhesive exhibits excellent adhesive strength, when the ultraviolet curable ink composition is used, the adhesive force between the bezel pattern and the upper base material can be improved.

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

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

In addition, the method for manufacturing a 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 to remove stains caused by foreign substances.

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

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 curable resin may be used instead of photolithography and screen printing. In order to apply the method, the viscosity of the ink composition of the present invention may be 1 cP to 50 cP, and preferably 3 cps to 45 cps.

An ink composition having a low viscosity of 1 cP to 50 cP is applied at a height of 0.1 to 20 μm, more specifically 0.5 to 5 μm, to form a bezel pattern on a specific portion of the substrate by the above method. 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 produced.

Light sources for curing the ultraviolet curable ink composition of the present invention include, but are not limited to, mercury vapor arcs, carbon arcs, Xe arcs, LED curing machines, etc., which emit light having a wavelength of 250 to 450 nm, for example. Do not.

The bezel pattern is characterized in that the taper angle measured after the curing treatment is more than 0 ° 30 °, thickness is 0.1㎛ ~ 20㎛. In addition, the taper angle may preferably be greater than 0 ° and 10 °. In addition, the thickness may be preferably 0.5㎛ ~ 5㎛. Since the bezel pattern of the present invention has the above characteristics, it may not exhibit deterioration of the luminous quality due to short circuit due to a large step, bubble generation, and mold release.

The optical density of the bezel pattern is 0.05 to 2.5 on the basis of the film thickness 1.0㎛, if necessary, may be 0.1 to 1.0. In this case, there is an advantage of excellent shielding characteristics by the bezel pattern. When the optical density exceeds 2.5, since the required content of the pigment to be added is very high, it may adversely affect the ink manufacturing and inkjet process, and may inhibit the UV curable ink composition from being cured by radiation.

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 edges of various devices such as a watch and a display device.

The optical density of the bezel pattern may be 0.05 to 2.5 per 1.0 μm film thickness, if necessary, 0.25 to 1.0. In this case, there is an advantage of excellent shielding characteristics by the bezel pattern. When the optical density exceeds 2.5, since the required content of the pigment to be added is very high, it may adversely affect the ink manufacturing and inkjet process, and may inhibit the UV curable ink composition from being cured by radiation.

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), a thin film transistor liquid crystal The display device may be used in any one of a thin film transistor-liquid crystal display (LCD-TFT) and a cathode ray tube (CRT).

Hereinafter, an Example is given and this invention is demonstrated in detail. The following examples are provided to illustrate the present invention, and the scope of the present invention includes the ranges described in the following claims, their substitutions and changes, and is not limited to the examples.

Table 1

	coloring agent	Epoxy	Oxetane	Polymerization initiator	Surfactants	diluent	Photosensitizer
Example	A	B	C	D	E	G	H
One	A1: 5	B1: 13	C2: 76	D1: 5	E1: 1	-	-
2	A1: 5	B1: 18	C2: 71	D1: 5	E1: 1	-	-
3	A1: 4	B1: 57	C2: 33	D1: 5	E1: 1	-	-
4	A1: 5	B1: 40	C2: 49	D2: 5	E1: 1	-	-
5	A1: 5	B1: 40	C2: 49	D3: 5	E1: 1	-	-
6	A1: 5	B1: 40	C2: 49	D4: 5	E1: 1	-	-
7	A1: 5	B1: 40	C2: 49	D5: 5	E1: 1	-	-
8	A1: 5	B1: 20 B2: 10	C3: 59	D3: 5	E1: 1	-	-
9	A1: 5	B3: 40	C2: 49	D3: 5	E1: 1	-	-
10	A1: 5	B1: 20 B2: 10	C2: 59	D3: 5	E2: 1	-	-
11	A1: 5	B1: 20 B2: 10	C2: 59	D3: 5	E3: 1		-
12	A1: 5	B1: 20 B2: 10	C2: 59	D3: 5	E4: 1		-
13	A1: 5	B2: 25	C2: 49	D3: 5	E4: 1	G1: 15	-
14	A1: 5	B1: 25	C2: 49	D3: 5	E4: 1	G1: 15	-
15	A1: 5	B1: 30.5	C2: 58	D4: 5	E3: 1	-	H1: 0.5
16	A1: 5	B1: 30.5	C2: 58	D1: 5	E3: 1	-	H1: 0.5
17	A1: 5	B1: 30.5	C2: 58	D3: 5	E3: 1	-	H2: 0.5
18	A1: 5	B1: 20	C1: 10 C2: 59	D1: 5	E2: 1	-	-
19	A1: 5	B1: 20	C3: 10 C2: 59	D3: 5	E2: 1	-	-
20	A1: 5	B1: 20	C3: 5C2: 64	D5: 5	E2: 1	-	-
21	A1: 5	B3: 15	C1: 15 C2: 59	D1: 5	E3: 1	-	-
Comparative example						-	-
One	A1: 5	B1: 10	C2: 79	D5: 5	E2: 1	-	-
2	A1: 5	B1: 65	C2: 24	D3: 5	E2: 1	-	-
3	A1: 5	B1: 12	C2: 77	D3: 5	E2: 1	-	-
4	A1: 5	B1: 8	C2: 81	D3: 5	E2: 1	-	-
5	A1: 5	B2: 40	C2: 50	D3: 5	-	-	-
6	A1: 5	B2: 40	C2: 49	D3: 5	E5: 1	-	-
7	A1: 5	B2: 35	C2: 19	D1: 5	E1: 1	G1: 35	-
8	A1: 5	B3: 35	C2: 19	D1: 5	E1: 1	G1: 35	-
9	A1: 5	B1: 65	C2: 24	D1: 5	E1: 1	-	-
10	A1: 5	B1: 65	C2: 24	D3: 5	E1: 1	-	-
11	A1: 5	B1: 10	C2: 79	D4: 5	E1: 1	-	-
12	A1: 5	B1: 15	C3: 44 C2: 30	D1: 5	E3: 1	-	-
13	A1: 5	B3: 15	C3: 44 C4: 30	D1: 5	E3: 1	-	-
14	A1: 5	B1: 15	C1: 44 C4: 30	D1: 5	E1: 1	-	-
15	A1: 35	B1: 5	C2: 19	D1: 5	E1: 1	G1: 35	-
16	A1: 0.1	B1: 25	C2: 68.9	D1: 5	E1: 1	-	-

A1: carbon black

B1: CELLOXIDE 2021P (DICEL CORPORATION)

B2: YD-128 (bisphenol A diglycidyl ether, Kukdo Chemical)

B3: CELLOXIDE 3000 (DICEL CORPORATION)

C1: Aaron Oxetane 101 (Toagosei)

C2: Aaron Oxetane 221 (Toagosei)

C3: Aaron Oxetane 212 (Toagosei)

C4: Aaron Oxetane 121 (Toagosei)

D1: CPI-200K (San-Afro)

D2: Irgacure 290 (BASF)

D3: UV-694 (Tetrachem)

D4: Rhodorsil 2074 (Blue Star Silicon)

D5: Irgacure 250 (BASF)

E1: BYK-330 (BYK chemie)

E2: BYK-3441 (BYK chemie)

E3: RS-75 (DIC)

E4: F-561 (DIC)

E5: F-472SF (DIC)

G1: propylene glycol monomethyl ether acetate

H1: 9,10-dibutoxyanthracene

H2: 2-isopropyl thioxanthone

Production Example 1 Preparation of Bezel Pattern

The compositions prepared in Examples 1 to 21 and Comparative Examples 1 to 14 were coated on the cleaned LCD glass substrate by an inkjet coating method so as to have 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 UV under the following conditions within 1 minute after coating. UV irradiator used a high-pressure mercury lamp, and was irradiated with a light amount of 1000mJ / cm ² based on UVV.

Production Example 2 Fabrication of Display Device Using Bezel Pattern

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

Experimental Example 1 Viscosity

The viscosity of the compositions prepared in Examples 1 to 21 and Comparative Examples 1 to 14 was measured. Brookfield's DV-III + was used as a viscosity measuring instrument.

Experimental Example 2 Measurement of Curing Sensitivity and Taper Angle

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

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

(Triangle | delta): The bezel pattern was hardened, but there was stickiness

×: hardening of the bezel pattern was insufficient, resulting in unreacted residue

In addition, a cross-sectional SEM photograph of the bezel pattern was taken, and taper angle measurements were performed. The results are shown in Table 2 below.

○: taper angle 10 degrees or less

△: taper angle is 10 degrees or 30 degrees

X: taper angle more than 30 degrees

Experimental Example 3: Bezel Pattern OD Evaluation

In the method of Preparation Example 1, the OD of the composition coated on a general LCD glass substrate by 1 μm in thickness by spin coating instead of inkjet coating was measured using an OD meter manufactured by X-rite.

TABLE 2

Example	Viscosity	Hardening	Taper angle	OD value
Condition	(cP)	5 minutes after UV irradiation, O: tack-freeΔ: tack feeling X: unreacted	Taper O: <10 ° △: 10 ° to 30 ° X:> 30 °	/ 1㎛
One	14	O	O	0.3
2	17	O	O	0.3
3	45	O	O	0.25
4	32	O	O	0.3
5	32	O	O	0.3
6	32	O	O	0.3
7	32	O	O	0.3
8	39	△	O	0.3
9	7	O	O	0.3
10	44	O	O	0.3
11	44	O	O	0.3
12	45	O	O	0.3
13	40	O	O	0.3
14	15	O	O	0.3
15	23	O	O	0.3
16	23	O	O	0.3
17	23	O	O	0.3
18	16	O	O	0.3
19	14	O	O	0.3
20	16	O	O	0.3
21	18	O	O	0.3
Comparative example
One	13	△	O	0.3
2	67	O	O	0.3
3	14	△	O	0.3
4	12	△	O	0.3
5	150	O	X	0.3
6	150	O	△	0.3
7	84	X	O	0.3
8	4	X	O	0.3
9	63	O	O	0.3
10	63	O	O	0.3
11	13	△	O	0.3
12	11	△	O	0.3
13	15	△	O	0.3
14	15	△	O	0.3
15	46	X	O	2.6
16	15	O	O	0.04

From the results of Table 2, the curable ink compositions of Examples 1 to 21 according to the present invention is cured even when the diluent is not used or the diluent is used in an amount of less than 20% by using an epoxy resin and an oxetane resin together. It can be seen that it is possible to produce a composition having excellent sensitivity. Compared with the ink compositions of Examples 1 to 4, the compositions of Comparative Examples 1, 3 and 4 with low epoxy content had insufficient curing sensitivity, and the compositions of Comparative Example 2 with excessive epoxy content had a viscosity of 50 cps or higher at room temperature. Therefore, applicability | paintability is inferior.

Although the ink compositions of Comparative Examples 5 and 6 had better curing sensitivities than the compositions of Comparative Examples 1 to 4, since the viscosity was very high compared to the compositions of Examples 1 to 21, high process temperatures of 70 degrees or more were required, and surfactants Poor taper angle due to improper selection of.

The ink compositions of Comparative Examples 7 and 8 had a lower viscosity but poorer curing sensitivity compared to the ink compositions of Examples 8 and 9 due to excessive use of a diluent.

The ink compositions of Comparative Examples 9 and 10 had a high viscosity, and the ink compositions of Comparative Examples 11 had insufficient curing sensitivity.

The compositions of Comparative Examples 12 to 14 had slightly better curing sensitivity than those of Comparative Examples 1 to 4, but the curing sensitivity was insufficient compared to the ink compositions of Examples.

Since the composition of Comparative Example 15 had an excessive content of a colorant, the curing sensitivity was very poor, and thus the curing was not performed by UV exposure alone, requiring a postbaking process. On the other hand, the composition of Comparative Example 16 was excellent in curing sensitivity, but the light shielding density of the cured product was low, so that sufficient hiding power could not be obtained.

Claims

Containing a colorant, an epoxy resin, an oxetane resin and a photopolymerization initiator,

The epoxy resin: ultraviolet curable ink composition in which the content ratio of oxetane resin is 1: 0.5 to 1: 6.
The method according to claim 1,

The ultraviolet curable ink composition further comprising any one or more selected from the group consisting of a surfactant, an adhesion promoter, a diluent and a photosensitizer.
The method according to claim 1,

The oxetane resin is an ultraviolet curable ink composition comprising an oxetane compound having one oxetane ring and an oxetane compound having two oxetane rings.
The method according to claim 3,

Oxetane compound having one oxetane ring: The ultraviolet curable ink composition, characterized in that the content ratio of the oxetane compound having two oxetane rings is 1:16 to 1: 3.
The method according to claim 1,

The content of the epoxy resin is UV curable ink composition, characterized in that 5 to 60% by weight relative to the total weight of the ultraviolet curable ink composition.
The method according to claim 1,

The content of the oxetane resin is UV curable ink composition, characterized in that 15 to 80% by weight relative to the total weight of the ultraviolet curable ink composition.
The method according to claim 1,

The photopolymerization initiator is an ultraviolet curable ink composition, characterized in that the iodonium salt or sulfonium salt.
The method according to claim 1,

The content of the photopolymerization initiator is UV curable ink composition, characterized in that 1 to 15% by weight based on the total weight of the ultraviolet curable ink composition.
The method according to claim 1,

The content of the colorant is UV curable ink composition, characterized in that 1 to 15% by weight based on the total weight of the ultraviolet curable ink composition.
The method according to claim 2,

The content of the diluent is UV curable ink composition, characterized in that 0 to 30% by weight based on the total weight of the ultraviolet curable ink composition.
The method according to claim 2,

The surfactant is an ultraviolet curable ink composition, characterized in that the silicone-based, fluorine-based or acrylic surfactant.
The method according to claim 2,

The surfactant is UV curable ink composition, characterized in that contained in 0.1 to 5.0% by weight relative to the total weight of the ultraviolet curable ink composition.
The method according to claim 2,

The photosensitizer is UV curable ink composition, characterized in that included in 1 to 200 parts by weight based on 100 parts by weight of the photopolymerization initiator.
The method according to claim 2,

The adhesion promoter is an ultraviolet curable ink composition, characterized in that the epoxy silane-based compound.
The method according to claim 2,

The adhesion promoter is an ultraviolet curable ink composition, characterized in that contained in 0.1 to 15% by weight relative to the total weight of the ultraviolet curable ink composition.
The method according to claim 1,

The cured dose of the said ultraviolet curable ink composition is 1-10,000 mJ / cm <2>, The ultraviolet curable ink composition characterized by the above-mentioned.
The method according to claim 1,

The viscosity of the ultraviolet curable ink composition is UV curable ink composition, characterized in that 1cp to 50cp at 25 ℃.
The method according to claim 17,

The viscosity of the ultraviolet curable ink composition is UV curable ink composition, characterized in that 3cp to 45cp at 25 ℃.
The method according to claim 1,

The taper angle after hardening of the said ultraviolet curable ink composition is 0 degrees-30 degrees, The ultraviolet curable ink composition characterized by the above-mentioned.
The method according to claim 19,

The taper angle is 0 ° ~ 10 ° UV curable ink composition, characterized in that.
The method according to claim 1,

The ultraviolet curable ink composition is ultraviolet curable ink composition, characterized in that the curing by absorbing radiation in the wavelength range of 250 nm to 450 nm.
The method according to claim 21,

The ultraviolet curable ink composition is ultraviolet curable ink composition, characterized in that the curing by absorbing radiation in the wavelength range of 360 nm to 410 nm.
The method according to claim 1,

The ultraviolet curable ink composition is a UV curable ink composition, characterized in that for forming a bezel pattern.
a) forming a bezel pattern on a substrate using the ultraviolet curable ink composition of claim 1; And

b) hardening the bezel pattern.
The method of claim 24,

The method of manufacturing a bezel pattern for a display substrate, further comprising the step of cleaning and drying the substrate before the forming the bezel pattern.
The method according to claim 25,

The cleaning and drying step of the substrate is a method of manufacturing a bezel pattern for a display substrate, characterized in that carried out by at least one treatment selected from the group consisting of wet surface treatment, UV ozone treatment, atmospheric pressure plasma treatment.
The method of claim 24,

The method of forming the bezel pattern on the substrate in step a) is a method of manufacturing a bezel pattern for a display substrate, characterized in that the method selected from inkjet printing, gravure coating and reverse offset coating .
The method of claim 24,

The step a) is a method of manufacturing a bezel pattern for a display substrate, characterized in that carried out at a process temperature of 10 ℃ to 100 ℃.
The method according to claim 28,

The step a) is a method of manufacturing a bezel pattern for a display substrate, characterized in that carried out at a process temperature of 20 ℃ to 70 ℃.
The method of claim 24,

The step b) is a method of manufacturing a bezel pattern for a display substrate, characterized in that the curing by absorbing radiation in the wavelength range of 250 nm to 450 nm.
The method of claim 30,

The step b) is a method of manufacturing a bezel pattern for a display substrate, characterized in that the curing by absorbing radiation in the wavelength range of 360 nm to 410 nm.
The method of claim 24,

The bezel pattern manufacturing method of the bezel pattern for a display substrate, characterized in that the thickness of 0.1㎛ ~ 20㎛.
The method according to claim 32,

The thickness of the bezel pattern is 0.5㎛ ~ 5㎛ manufacturing method of the bezel pattern for a display substrate.
The method of claim 24,

The taper angle of the bezel pattern is a manufacturing method of the bezel pattern for a display substrate, characterized in that 0 ° ~ 30 °.
The method of claim 34, wherein

The taper angle of the bezel pattern is a manufacturing method of the bezel pattern for a display substrate, characterized in that 0 ° ~ 10 °.
The method of claim 24,

The method of manufacturing a bezel pattern for a display substrate, characterized in that the OD value of the bezel pattern is 0.05 ~ 2.5 per 1.0 ㎛ thickness.
The bezel pattern for display substrates which hardened | cured the ultraviolet curable ink composition of Claim 1 and formed on the board | substrate.
The method of claim 37,

A bezel pattern for a display substrate, wherein the bezel pattern has a thickness of 0.1 μm to 20 μm.
The method of claim 38,

A bezel pattern for a display substrate, wherein the bezel pattern has a thickness of 0.5 μm to 5 μm.
The method of claim 37,

A bezel pattern for a display substrate, wherein the taper angle of the bezel pattern is 0 ° to 30 °.
The method of claim 40,

A bezel pattern for a display substrate, wherein the taper angle of the bezel pattern is 0 ° to 10 °.
The method of claim 37,

The bezel pattern for a display substrate, characterized in that the OD value of the bezel pattern is 0.05 ~ 2.5 per 1.0 ㎛ thickness.