WO2016048118A1 - Uv-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby - Google Patents

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 surfactant comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator, and a polar functional group, wherein the content ratio of the epoxy resin to the oxetane resin is 1:0.5-1:6, an adhesion to a glass substrate after curing is 4B or higher according to the ASTM D3359 standard, a contact angle to the glass substrate is less than 10°, and an adhesion with a substrate coated with an adhesive layer after curing is 100-5,000gf/25mm.

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 -0138097, 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 display devices, in order to achieve weight reduction and thinning, a method of forming a bezel pattern on a substrate is used instead of using a separate bezel structure.

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, the thickness of the formed pattern is increased to several tens of micrometers due to the high viscosity of the composition, which results in a step between the pattern forming portion and the pattern non-forming portion. In addition, the bezel portion having a color such as white or gold in addition to the black color is used to form the bezel portion by using a method of overcoating several times to obtain an optical density of an appropriate level. Similarly, as the printing frequency of the bezel pattern increases, the level difference between the pattern forming portion and the non-forming portion increases.

In particular, in the case of a touch panel display in which a bezel pattern is disposed on an inner surface of a display device, a problem occurs in that the conductive film is intermittently coated or short-circuited when the transparent conductive film is coated. In addition, when attaching an upper substrate such as a film coated with a pressure-sensitive adhesive on the bezel film, if the adhesion between the film and the bezel is not sufficient, bubble generation and film peeling problems may occur. Therefore, it is necessary to develop a method for forming a bezel pattern which is superior in adhesion with a film as compared with the conventional method for forming a bezel pattern.

In order to solve the problems of the prior art, the present invention, when cured by forming a bezel pattern using a UV curable ink composition having a small taper angle, a thin film thickness and a high adhesion to the film coated with the adhesive, bubble generation and film An object of the present invention is to provide a method of manufacturing a bezel pattern to minimize the release of the bezel pattern, and a display substrate including the same.

This invention contains surfactant containing a coloring agent, an epoxy resin, an oxetane resin, a photoinitiator, and a polar functional group, The content ratio of the said epoxy resin: oxetane resin is 1: 0.5-1: 6, and glass after hardening The adhesive force to the substrate is 4B or more according to ASTM D3359 standard, the contact angle to the glass substrate is less than 10 °, and provides an ultraviolet curable ink composition having an adhesive force with the substrate coated with an adhesive layer after curing is 100 ~ 5000gf / 25mm.

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 by using a UV curable ink composition comprising a surfactant containing a polar functional group, the prepared bezel pattern is excellent in adhesion and coating property to the glass substrate, it is attached to the bezel film and the top Excellent adhesion to the substrate.

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

This invention contains surfactant containing a coloring agent, an epoxy resin, an oxetane resin, a photoinitiator, and a polar functional group, The content ratio of the said epoxy resin: oxetane resin is 1: 0.5-1: 6, and glass after hardening It provides an ultraviolet curable ink composition in which the adhesion to the substrate is 4B or higher in the ASTM D3359 standard, the contact angle to the glass substrate is less than 10 °, and the adhesion between the bezel film and the substrate attached to the top is 100 to 5000 gf / 25mm.

In addition, the ultraviolet curable ink composition of the present invention may further include any one or more selected from the group consisting of adhesion promoters, colorants 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, Daicel Co., Ltd. Celoxide 8000 etc. can be used.

The content of the epoxy resin is preferably 5 to 50% by weight, more preferably 10 to 30% by weight based on the total weight of the ultraviolet curable ink composition. When it exceeds 50 weight%, coating property will fall, and when it is less than 5 weight%, a 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 75% by weight, and more preferably 40 to 60% by weight based on the total weight of the ultraviolet curable ink composition. If it exceeds 75% by weight, the curing degree is low, and if it is less than 15% by weight, the viscosity rises and the coating property is lowered.

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, the oxetane compound having one oxetane ring: The content range of the oxetane compound having two oxetane rings is in the range of 1: 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 ultraviolet curable ink composition includes a surfactant containing a polar functional group to lower the surface tension of the ink composition in order to exhibit a small taper angle. The surfactant including the polar functional group may include any one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate salt and a sulfonate salt.

Most conventional silicone surfactants have excellent coating property on the substrate and have a small taper angle. However, after applying the ink composition on the substrate to form a bezel part pattern, the adhesive-coated film including the polarizing plate may be attached. When the adhesion between the substrate and the film is lowered, a defect may occur. On the other hand, non-silicone and fluorine-based surfactants have the advantage of excellent adhesion between the bezel portion formed on the substrate and the adhesive coated film, the adhesive coated film is not limited to a polarizing plate or nichiban tape, a release film. In particular, surfactants containing a hydroxyl group (OH-) and a carboxyl group (COOH-) including a polar reactor are particularly preferably used in terms of adhesion since they have high affinity with the pressure-sensitive adhesive component. More preferably, hydrophilic fluorine-based surfactants or non-silicone-based surfactants or silicone-based surfactants containing hydroxyl groups are used to improve the coating property on the substrate.

Specifically, the surfactant may be a polymer or oligomeric fluorine-based surfactant, it is possible to use a very non-polar (solubility parameter value less than 15 (MPa) ^0.5 ) solvent, for example, insoluble in Hexane. In addition, the surfactant may be a polymeric or oligomeric fluorine-based surfactant, and may be used in a highly polar solvent (solubility parameter value of 45 (MPa) ^0.5 or more), for example, insoluble in water at least 0.1 wt%. have. In addition, the surfactant may be a polymer or oligomeric fluorine-based surfactant, and can be dissolved in more than 1 wt% in an appropriate polar solvent (solubility parameter value of about 21 (MPa) ^0.5 ), for example, propyelne glycol monomethyl ether. One without phase separation can be used. In addition, the surfactant may be a polymer or oligomeric fluorine-based surfactant, and also can be dissolved in an appropriate polar solvent (for example, toluene of 0.1 (MPa) ^0.5 or more) of 0.1 wt% or more and phase separation You can use the missing one. The appropriate polarity value may be a solubility parameter value of 15 to 21 (MPa) ^0.5 .

The surfactant is preferably a polymer or oligomeric fluorine-based surfactant, not dissolved in a solvent having a solubility parameter value of less than 15 (MPa) ^0.5 , and 0.1 weight in a solvent having a solubility parameter value of 45 (MPa) ^0.5 or more. It may be used that does not dissolve more than%, dissolve more than 1% by weight in a solvent having a solubility parameter value of 15 to 21 (MPa) ^0.5 and no phase separation.

In addition, the surfactant may be a surfactant containing a reactive hydroxyl group as a silicone-based additive. In addition, the surfactant may be a non-silicone surfactant that does not contain a fluorine component.

As the fluorine-based surfactant, the non-silicone-based surfactant and the silicon-based surfactant including a hydroxyl group, commercially available products may be used, for example, Megaface F-251, F-281, F-560, F, manufactured by DaiNippon Ink & Chemicals (DIC). -561, F-562, F-563, F-565, F-568, F-570 and F-571 or Surflon S-111, S-112, S-113, S-121, S- from Asahi Glass. 131, S-132, S-141 and S-145 or Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 and FC-4430 from Sumitomo SriM Or Zonyl FS-300, FSN, FSN-100 and DuPont's BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYKETOL-AQ, BYK-DYNWET 800, etc. can be used.

The surfactant containing the polar functional group 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 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 (Degussa Co., Ltd.); 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 long wavelength ultraviolet light (for example, 365 or 395 nm), and is characterized by having a certain level of optical density (OD). 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 may be maintained in the range of 0.05 to 2.5 per 1.0 μm of the film thickness.

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

The colorants 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 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 colorant is preferably 0 to 30% by weight, and more preferably 8 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 may further include a photosensitizer to compensate for the sclerosis in the long wavelength active energy ray.

The photosensitizers are anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxy

Anthracene-based compounds such as anthracene, 9,10-diethoxy anthracene 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 on 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 substrate. In order to prevent this, 1 selected from the group consisting of amino silane compounds, alkoxy silane compounds, epoxy silane compounds, aminophenyl silane compounds, amino silane compounds, mercapto silane compounds and vinyl silane compounds as adhesion promoters Excellent results can be obtained when more than one silane compound is used.

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

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

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. The excellent spreadability of the ultraviolet curable ink composition of the present invention may specifically indicate that the contact angle to the glass substrate is less than 10 °. 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 process temperature means a temperature heated so that the curable ink composition can be smoothly discharged through the inkjet head. The process temperature may be 10 ° C to 100 ° C, preferably 20 ° C to 70 ° C.

The adhesive force with respect to the glass base material of the bezel pattern formed using the ultraviolet curable ink composition of this invention is 4B or more in ASTM D3359 standard, and is excellent in adhesive force and coating property.

In addition, the ultraviolet curable ink composition includes a surfactant including a polar functional group, so that the bezel pattern formed according to the present invention has excellent adhesion to a film substrate coated with an adhesive. Specifically, the adhesive force between the bezel and the film-coated film substrate after curing of the ultraviolet curable ink composition of the present invention is 100 to 5000 gf / 25mm based on the peel strength by a 180-degree peel test. It can have a value of.

The upper end of the bezel pattern formed of the ultraviolet curable ink composition is attached to the polarizing plate through the pressure-sensitive adhesive layer for the polarizing plate, the ultraviolet curable ink composition is an acrylic pressure sensitive adhesive, styrene butadiene rubber pressure sensitive adhesive, epoxy pressure sensitive adhesive, polyvinyl alcohol pressure sensitive adhesive, polyurethane type Since the adhesive for films such as pressure-sensitive adhesives and the like excellent adhesive force, when using the UV-curable ink composition can be obtained an effect of improving the adhesion between the bezel pattern and the film coated with the adhesive including the polarizing plate. In this invention, an upper base material is not limited to a polarizing plate or a protective film.

Since the adhesive force may be measured differently according to the type of the adhesive applied to the film, the standard for measuring the adhesive force between the bezel pattern and the upper substrate described in the present invention using Nichiban CT-24 tape used in Japanese Industrial Standard JIS Z 1522 Based on the measured peel strength value. At this time, the adhesive force property having the adhesive force between the bezel pattern and the upper substrate in the range of 100 to 5000 gf / 25 mm belongs to the characteristic category of the present invention.

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.

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. The excellent spreadability of the ultraviolet curable ink composition of the present invention may specifically indicate that the contact angle to the glass substrate is less than 10 °. 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.

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 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 ultraviolet curable ink composition of the present invention includes a surfactant containing a polar functional group, so that the bezel pattern formed according to the present invention has excellent adhesion to the polarizing plate. Specifically, the upper adhesion after curing of the ultraviolet curable ink composition of the present invention may have a value of 100 ~ 5000gf / 25mm.

The bezel pattern formed according to the present invention is excellent in adhesion to the glass substrate after curing treatment, 4B or more in the ASTM D3359 standard.

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 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 0.1 to 5 on the basis of the film thickness of 2.0㎛, if necessary, may be 0.5 to 2. In this case, there is an advantage of excellent shielding characteristics by the bezel pattern. When the optical density exceeds 5, the required content of the pigment to be added is very high, which may adversely affect the ink production and inkjet process, and may inhibit the UV curable ink composition from being cured by radiation.

In addition, the ultraviolet curable ink composition of the present invention includes a surfactant containing a polar functional group, so that the bezel pattern formed according to the present invention has excellent adhesion to the polarizing plate. Specifically, the upper adhesion after curing of the ultraviolet curable ink composition of the present invention may have a value of 100 ~ 5000gf / 25mm.

The said bezel pattern is excellent in the adhesive force with respect to the glass base material after hardening process being more than 4B by ASTM D3359 standard.

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.

<Example>

To be mixed in the same composition as in Table 1, and stirred for 3 hours to prepare a composition for forming bezel patterns of Examples 1 to 4 and Comparative Examples 1 and 2.

Table 1 coloring agent Epoxy Oxetane Polymerization initiator Surfactants Adhesion promoter Example A B C D E F One A1: 3 B1: 15 C1: 77 D1: 3 E1: 1 F1: 1 2 A1: 3 B1: 15 C1: 77.5 D1: 3 E2: 0.5 F1: 1 3 A1: 5 B1: 25 C1: 64.5 D1: 3 E3: 1.5 F2: 1 4 A1: 3 B1: 15 C1: 77 D1: 3 E4: 1 F3: 1 Comparative example One A1: 3 B1: 15 C1: 78 D1: 3 - F3: 1 2 A1: 3 B1: 15 C1: 73 D1: 3 E5: 5 F3: 1

A1: carbon black

B1: CELLOXIDE 2021P (DICEL CORPORATION)

C1: Aaron Oxetane 221 (Toagosei)

D1: SP-150 (Asahi Denka)

E1: RS-75 (DIC)

E2: BYK-388 (BYK chemie)

E3: F-484 (DIC)

E4: BYK-3441 (BYK chemie)

E5: BYK-330 (BYK chemie)

F1: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

F2: 3-methacryloxypropyl triethoxysilane

F3: 8-methacryloxyoctyltrimethoxysilane

Production Example 1 Preparation of Bezel Pattern

The compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 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. The ultraviolet irradiator used a high-pressure mercury lamp having a wide ultraviolet emission wavelength range. After irradiating 1000mJ / cm ² ultraviolet rays, latex gloves were worn to determine whether the bezel pattern was cured, and then pressed to observe indentation and tack.

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 4 and Comparative Examples 1 to 2 was measured. Brookfield's DV-III + was used as a viscosity measuring instrument.

Experimental Example 2 Measurement of Curing Sensitivity

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

<Experiment 3>: spreadability evaluation

After applying the composition prepared in Examples 1 to 4 and Comparative Examples 1 and 2 on the washed LCD glass substrate, the contact angle was measured.

Experimental Example 4 Evaluation of Adhesion between Film / Bezel Patterns

A polarizing film having a width of 25 mm and a length of 50 to 100 mm to which an adhesive layer was applied was attached to a bezel pattern at room temperature using a roll laminator. The peel strength measurement results when the film was peeled off the bezel by performing a 180 ° peel test are shown in Table 2 below.

Experimental Example 5 Cross-hatch Adhesion

The bezel pattern manufactured in Preparation Example 1 was subjected to a cross cut test in accordance with the standard of ASTM D3359, which is a cross cut test criterion. Before performing the cross cut test, the heat treatment may be performed for 1 minute at a temperature of 60 degrees to facilitate the reaction of the adhesion promoter depending on the sample. Specifically, the specimens were cut in 11 rows in the horizontal and vertical directions at intervals of 1 mm, respectively, to form 100 square grids each having a width of 1 mm. Then, when the CT-24 adhesive tape of Nichiban Co., Ltd. was attached to the cut surface and then peeled off, the state of the faces falling together was measured and evaluated according to the following criteria.

<Cross-Hatch Adhesive Evaluation Criteria>

5B: If no faces fall

4B: If the faces fall within 5% of the total area

3B: 5-15% of total surface area

2B: 15 to 35% of total area apart

1B: 35 to 65% of total surface area

0B: almost everything falls

TABLE 2 Example Viscosity Hardening Spreadability Upper adhesion Adhesion (at 5 minutes) Condition (cP) 5 minutes after UV irradiation, O: tack-freeΔ: tack feeling X: unreacted Contact angle O: <10 ° △: 10 ° to 30 ° X:> 30 ° peel test (Nichiban tape) Cross cut test One 16 O O 500-1500 4B 2 16 O O 1500-2500 4B 3 24 O O 500-1000 4B 4 16 O O 1000-1500 4B Comparative example One 16 O X 100-200 4B 2 15 O O 10-50 4B

As a result of the experiment, the ink compositions of Examples 1 to 4 using a surfactant containing a polar functional group showed a low contact angle and had a high upper adhesion, whereas the ink compositions of Comparative Example 1 using a surfactant containing a polar functional group were not used. The ink composition exhibits a high contact angle, and there is a problem that the ink composition of Comparative Example 2 has a low top adhesion.

Claims (48)

A surfactant comprising a colorant, an epoxy resin, an oxetane resin, a photopolymerization initiator, and a polar functional group, The content ratio of the epoxy resin: oxetane resin is 1: 0.5 to 1: 6, The adhesion to the glass substrate after curing is 4B or more in ASTM D3359 standard, the contact angle to the glass substrate is less than 10 °, UV curable ink composition with top adhesion after curing of 100 to 5000 gf / 25mm The method according to claim 1, An ultraviolet curable ink composition further comprising any one or more selected from the group consisting of adhesion promoters, colorants and photosensitizers. The method according to claim 1, The surfactant including the polar functional group includes any one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphoric acid group and a sulfonic acid group. The method according to claim 3, The surfactant is a polymer or oligomeric fluorine-based surfactant, does not dissolve in a solvent having a solubility parameter value of less than 15 (MPa) ^0.5 , does not dissolve at least 0.1% by weight in a solvent having a solubility parameter value of 45 (MPa) ^0.5 or more, UV curable ink composition characterized in that the solubility parameter value is dissolved in a solvent having a value of 15 to 21 (MPa) ^0.5 or more% by weight and no phase separation. The method according to claim 4, The solvent having a solubility parameter value of less than 15 (MPa) ^0.5 is hexane, the solvent having a solubility parameter value of 45 (MPa) ^0.5 or more is water, and the solvent having a solubility parameter value of 15 to 21 (MPa) ^0.5 is PGME (propyelne). glycol monomethyl ether) or toluene, UV curable ink composition. The method according to claim 3, The surfactant is a UV curable ink composition, characterized in that the surfactant containing a reactive hydroxyl group as a silicone-based additive. The method according to claim 3, Said surfactant is a non-silicone type surfactant which does not contain a fluorine component, The ultraviolet curable ink composition characterized by the above-mentioned. The method according to claim 3, The surfactant including the polar functional group 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 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 9, 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 50% 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 an ultraviolet curable ink composition, characterized in that 15 to 75% 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 colorant 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 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 at least one silane selected from the group consisting of amino silane compounds, alkoxy silane compounds, epoxy silane compounds, aminophenyl silane compounds, amino silane compounds, mercapto silane compounds and vinyl silane compounds. UV-curable ink composition, characterized in that the 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 21, 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 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 26, The method of manufacturing a bezel pattern for a display substrate further comprising the step of cleaning and drying the substrate before forming the bezel pattern. The method of claim 27, 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 26, 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 26, 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 of claim 30, 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 26, Method of manufacturing a bezel pattern for a display substrate, characterized in that the upper adhesion of the bezel pattern of step b) is 100 to 5000gf / 25mm. The method of claim 26, Method for producing a bezel pattern for a display substrate, characterized in that the contact angle of the ultraviolet curable ink composition of step a) to the glass substrate is less than 10 °. The method of claim 26, Method for producing a bezel pattern for a display substrate, characterized in that the adhesive force of the bezel pattern of the glass substrate of step b) is 4B or more in ASTM D3359 standard. The method of claim 26, The bezel pattern manufacturing method of the bezel pattern for a display substrate, characterized in that the thickness of 0.1㎛ ~ 20㎛. The method of claim 35, wherein The thickness of the bezel pattern is 0.5㎛ ~ 5㎛ manufacturing method of the bezel pattern for a display substrate. The method of claim 26, 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 37, 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 26, 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 40, 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 41, 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 40, A bezel pattern for a display substrate, wherein the taper angle of the bezel pattern is 0 ° to 30 °. The method of claim 43, A bezel pattern for a display substrate, wherein the taper angle of the bezel pattern is 0 ° to 10 °. The method of claim 40, 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. The method of claim 40, The bezel pattern for the display substrate, characterized in that the upper adhesion of the bezel pattern is 100 to 5000gf / 25mm. The method of claim 40, A bezel pattern for a display substrate, wherein the contact angle with respect to the glass substrate is less than 10 degrees. The method of claim 40, A bezel pattern for a display substrate, characterized in that the adhesion to the glass substrate is more than 4B in ASTM D3359 standard.