UV-curable ink composition for forming bezel pattern having excellent reliability

Abstract

The present invention relates to an ultraviolet-curable ink composition for forming a bezel pattern, which has excellent curing sensitivity, can be easily photo-cured under atmospheric conditions, achieves excellent hardness, optical density and adhesion after curing, does not decrease in adhesion during reliability evaluation, and has little thickness reduction, thereby having improved reliability.

Description

Technical Field

[0001] This specification claims the benefit of the filing date of Korean Patent Application No. 10-2022-0184418 filed in the Korean Intellectual Property Office on December 26, 2022, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to an ultraviolet curable ink composition for forming a frame pattern with excellent reliability. Background Art

[0003] Display devices such as televisions and monitors are usually surrounded by metal wiring for driving the devices. In the past, independent frame structures were assembled to shield these wirings. However, in recent years, in order to achieve lightweight and thinner devices, methods such as inkjet printing have begun to be used to directly print black shading patterns on the substrate.

[0004] Furthermore, in recent years, there has been a growing demand for black patterns with excellent light-shielding properties, even at thin thicknesses, to prevent patterns and black patterns on mobile devices from being recognized. To address this, photocurable compositions with excellent curing sensitivity that can be easily cured with UV light under normal atmospheric conditions are being developed. Summary of the Invention

[0005] Technical issues

[0006] The present invention aims to provide a UV-curable ink composition for forming a frame pattern. The composition has excellent curing sensitivity and can be easily photocured under atmospheric conditions. After curing, it exhibits excellent optical density and adhesion properties. In reliability evaluations under high temperature and high humidity environments, it does not show a decrease in adhesion and has minimal thickness variation, thereby improving reliability.

[0007] Furthermore, the present invention is also directed to providing an ultraviolet curable ink composition for forming a frame pattern having improved heat resistance.

[0008] However, the technical problems of the present invention are not limited to the technical problems described above. Through the following description, those skilled in the art can clearly understand unmentioned or other technical problems.

[0009] Solutions to the Problem

[0010] One embodiment of the present invention provides a UV-curable ink composition for forming a frame pattern, which includes a pigment, a dispersant, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, a diglycidyl ether compound, a cationic initiator, and a free radical initiator.

[0011] Effects of the Invention

[0012] The ultraviolet curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent curing sensitivity and can be easily photocured under atmospheric conditions.

[0013] Furthermore, the ultraviolet curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent storage stability.

[0014] Furthermore, the UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent dispersibility and can easily dissolve additives such as a photoinitiator and a sensitizer.

[0015] Furthermore, the UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention can achieve excellent optical density and adhesion after curing.

[0016] Furthermore, the UV curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent reliability after curing, has no decrease in adhesion during reliability evaluation, and has little thickness variation.

[0017] Furthermore, the ultraviolet curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent heat resistance.

[0018] However, the effects of the present invention are not limited to the effects listed above, and various extended applications can be achieved without departing from the spirit and scope of the present invention. DETAILED DESCRIPTION

[0019] Best Mode for Carrying Out the Invention

[0020] Throughout this specification, when a component is referred to as “including (or comprising)” an element, unless expressly stated otherwise, instead of excluding any other elements, it may mean that a component may further include other elements.

[0021] Throughout this specification, when a component is described as being “on” another component, it includes not only a case where the component is directly in contact with the other component but also a case where other components are present therebetween.

[0022] Throughout this specification, “viscosity” may refer to a value measured by a Brookfield viscometer using a cone spindle (CPA-40Z) at room temperature (25° C.).

[0023] Throughout this specification, the unit "parts by weight" represents the weight ratio of each component.

[0024] Hereinafter, the present invention is described in further detail.

[0025] One embodiment of the present invention provides a UV-curable ink composition for forming a frame pattern, which includes a pigment, a dispersant, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, a diglycidyl ether compound, a cationic initiator, and a free radical initiator.

[0026] A UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention exhibits excellent curing sensitivity and can be readily photocured under atmospheric conditions. Specifically, the UV-curable ink composition for forming the frame pattern can be stably photocured without loss of curing sensitivity at temperatures between 18°C and 30°C, relative humidity between 15% and 45%, and in the absence of external stabilization conditions such as nitrogen aeration.

[0027] Furthermore, the ultraviolet curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent storage stability.

[0028] Furthermore, the UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent dispersibility and can easily dissolve additives such as a photoinitiator and a sensitizer.

[0029] Furthermore, the UV curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent reliability after curing, does not show a decrease in adhesion during reliability evaluation, and has little thickness variation.

[0030] According to one embodiment of the present invention, the above-mentioned UV-curable ink composition for forming a frame pattern includes a pigment, a dispersant, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, a diglycidyl ether compound and two photoinitiators (a cationic initiator and a free radical initiator). Specifically, the above-mentioned UV-curable ink composition for forming a frame pattern may not contain a solvent. That is, the above-mentioned UV-curable ink composition for forming a frame pattern may be a solvent-free UV-curable ink composition for forming a frame pattern. Here, the solvent refers to a reactive diluent commonly used in the art as an organic solvent for adjusting viscosity. Existing photocurable compositions for forming black patterns contain solvents. However, photocurable compositions containing solvents have problems such as poor storage stability, low hardness of the photocured material and low curing sensitivity. In contrast, the above-mentioned UV-curable ink composition for forming a frame pattern can improve storage stability because it does not contain a solvent. In addition, the photocured material of the above-mentioned UV-curable ink composition for forming a frame pattern that does not contain a solvent can have excellent hardness (for example, pencil hardness) after curing and can effectively improve adhesion to the substrate.

[0031] According to one embodiment of the present invention, the pigment may include a black pigment. As the black pigment, a black pigment used in the art can be used. For example, the black pigment may include at least one of carbon black, graphite, a metal oxide, and an organic black pigment, but the type of the black pigment is not limited.

[0032] For example, examples of the above-mentioned carbon black include SISTO 5HIISAF-HS, SISTO KH, SISTO 3HHAF-HS, SISTO NH, SISTO 3M, SISTO 300HAFLS, SISTO 116HMMAF-HS, SISTO 116MAF, SISTO FMFEF-HS, SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTOSSRF manufactured by Donghae Carbon Co., Ltd.; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram Black LH, Diagram Black HA, Diagram Black SF, Diagram Black N550M, Diagram Black M, Diagram Black E, Diagram Black G, Diagram Black R, Diagram Black N760M, Diagram Black 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; PRINTEX-U, PR manufactured by Degussa, Co., Ltd. INTEX-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, SPECIALBLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK-101; and Columbia Carbon, Co., Ltd.Manufactured RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAV EN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170, or mixtures thereof. Furthermore, as the organic black pigment, aniline black, lactam black, or perylene black series can be used, but are not limited thereto.

[0033] According to one embodiment of the present invention, the content of the pigment can be from 5 parts by weight to 20 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the pigment can be from 6.5 parts by weight to 17.5 parts by weight, from 8 parts by weight to 16 parts by weight, from 8 parts by weight to 15 parts by weight, from 8 parts by weight to 13 parts by weight, from 8 parts by weight to 11 parts by weight, from 10 parts by weight to 16.5 parts by weight, from 10 parts by weight to 15 parts by weight, from 10 parts by weight to 12.5 parts by weight, or from 10 parts by weight to 11 parts by weight. When the content of the pigment in the UV-curable ink composition is within the above range, the photocured product of the UV-curable ink composition for forming a frame pattern can exhibit a uniform color without reducing the curing sensitivity of the UV-curable ink composition for forming a frame pattern.

[0034] In particular, when the content of the aforementioned pigment is within the aforementioned range, the aforementioned UV-curable ink composition for forming a frame pattern can achieve a desired optical density after curing. Furthermore, the aforementioned pigment can be effectively prevented from not being dispersed in the UV-curable ink composition for forming a frame pattern, thereby forming precipitates. Furthermore, degradation of process performance due to nozzle clogging, etc., during the inkjet process, can be prevented.

[0035] According to one embodiment of the present invention, the dispersant may include a polyurethane compound. That is, the dispersant may include a compound having a polyurethane bond. Specifically, the dispersant contained in the UV-curable ink composition may be a polyurethane dispersant. By adding a dispersant containing a polyurethane compound to the UV-curable ink composition, the dispersibility of the pigment, oxetane compound, alicyclic epoxy compound, vinyl ether compound, diglycidyl ether compound, photoinitiator, and additive contained in the UV-curable ink composition for forming a frame pattern can be improved, thereby providing a UV-curable ink composition for forming a frame pattern having a uniform composition. As a result, the photocured material of the UV-curable ink composition for forming a frame pattern can effectively improve its hardness and adhesion to the substrate. In addition, since the UV-curable ink composition for forming a frame pattern includes a polyurethane dispersant, the pigment can be uniformly dispersed in the UV-curable ink composition for forming a frame pattern, while improving the curing efficiency and achieving a uniform color distribution.

[0036] According to one embodiment of the present invention, the polyurethane compound included in the dispersant may be a compound commonly used in the art. For example, the polyurethane dispersants Disperbyk 160 to 167 and 182 series may be used, but the type of the polyurethane dispersant is not limited.

[0037] According to one embodiment of the present invention, the dispersant may not include an acrylic dispersant. When an acrylic dispersant is included as a dispersant, the hardness (e.g., pencil hardness) and adhesion of the photocured product of the UV-curable ink composition for forming a frame pattern may decrease. In contrast, the UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention includes a polyurethane compound as a dispersant, thereby effectively improving its hardness and adhesion after curing.

[0038] According to one embodiment of the present invention, the content of the dispersant may be from 1 part by weight to 6 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the dispersant may be from 2 parts by weight to 5.5 parts by weight, from 2 parts by weight to 5 parts by weight, from 2 parts by weight to 4 parts by weight, from 2 parts by weight to 3 parts by weight, from 2.25 parts by weight to 5 parts by weight, from 2.25 parts by weight to 4 parts by weight, from 2.25 parts by weight to 3 parts by weight, from 2.25 parts by weight to 2.75 parts by weight, from 2.5 parts by weight to 4.0 parts by weight, from 2.5 parts by weight to 3.5 parts by weight, from 2.5 parts by weight to 3 parts by weight, or from 2.5 parts by weight to 2.75 parts by weight. By adjusting the dispersant content in the UV-curable ink composition within the aforementioned range, the dispersibility of the UV-curable ink composition can be improved, thereby ensuring that the UV-curable ink composition for forming a frame pattern has a uniform composition. Furthermore, the pigment can be evenly dispersed in the UV-curable ink composition for forming a frame pattern, improving curing efficiency while achieving a uniform color distribution. Furthermore, the hardness and substrate adhesion of the photocured product of the UV-curable ink composition for forming a frame pattern can be effectively improved.

[0039] According to one embodiment of the present invention, the above-mentioned ultraviolet curable ink composition for forming a frame pattern may contain an oxetane compound. Specifically, the above-mentioned oxetane compound may contain one or more oxetane rings in the molecule. More specifically, the number of oxetane rings contained in the above-mentioned oxetane compound molecule may be more than 1 and less than 4, more than 1 and less than 3, more than 1 and less than 2, or 1. By using an oxetane compound containing an oxetane ring within the above-mentioned range, the curing sensitivity, storage stability and dispersibility of the above-mentioned ultraviolet curable ink composition for forming a frame pattern can be improved. In addition, the optical density, hardness and adhesion of the photocured product of the above-mentioned ultraviolet curable ink composition for forming a frame pattern can also be effectively improved.

[0040] According to one embodiment of the present invention, the oxetane compound may include at least one of an aliphatic oxetane compound and an aromatic oxetane compound. Specifically, the oxetane compound may include at least one of a compound represented by the following Chemical Formula 1-1 and a compound represented by the following Chemical Formula 1-2. More specifically, the oxetane compound may be a compound represented by the following Chemical Formula 1-1.

[0041] [Chemical Formula 1-1]

[0042]

[0043] [Chemical formula 1-2]

[0044]

[0045] In the above chemical formula 1-1, R1 and R4 can each independently be a straight chain or branched chain alkyl group having 1 to 10 carbon atoms, R2 and R3 can each independently be a straight chain or branched chain alkylene group having 1 to 5 carbon atoms, and n1 can be 0 or an integer from 1 to 4. Specifically, R1 and R4 can each independently be a straight chain or branched chain alkyl group having 1 to 8 carbon atoms, a straight chain or branched chain alkyl group having 2 to 6 carbon atoms, or a straight chain or branched chain alkyl group having 5 to 10 carbon atoms. In addition, R1 and R3 can each independently be a straight chain or branched chain alkylene group having 1 to 3 carbon atoms, or a straight chain or branched chain alkylene group having 1 to 2 carbon atoms. The above n1 can be 0 or an integer from 1 to 2, 1 or 0.

[0046] In the above chemical formula 1-2, R5 and R 10 R6 to R9 may each independently be a linear or branched alkyl group having 1 to 10 carbon atoms, Ar1 may be an arylene group having 6 to 20 carbon atoms, and n2 may be an integer from 1 to 4. Specifically, R5 and R 10 Each of R6 to R9 can be independently a straight chain or branched chain alkyl group having 1 to 8 carbon atoms, a straight chain or branched chain alkyl group having 2 to 6 carbon atoms, or a straight chain or branched chain alkyl group having 2 to 4 carbon atoms. In addition, R6 to R9 can be independently a straight chain or branched chain alkylene group having 1 to 3 carbon atoms, or a straight chain or branched chain alkylene group having 1 to 2 carbon atoms. In addition, Ar1 can be an arylene group having 6 to 18 carbon atoms, an arylene group having 6 to 15 carbon atoms, an arylene group having 6 to 10 carbon atoms, or benzene.

[0047] By using an oxetane compound containing at least one of the compound represented by Chemical Formula 1-1 and the compound represented by Chemical Formula 1-2, a UV-curable ink composition for forming a frame pattern can be achieved with excellent curing sensitivity, storage stability, and dispersibility. Furthermore, the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion after curing.

[0048] The oxetane compound may include at least one of the following compounds 1-1 to 1-3. Specifically, the oxetane compound may be the following compound 1-1.

[0049] [Compound 1-1]

[0050]

[0051] [Compound 1-2]

[0052]

[0053] [Compounds 1-3]

[0054]

[0055] In the above-mentioned compound 1-3, n is an integer of 1 to 4.

[0056] In addition, the above-mentioned oxetane compound may also include at least one of 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetane)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetane)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-cyclohexyloxymethyloxetane and novolac epoxyoxetane. As the oxetane compound, for example, "Alonoxetane OXT-101", "Alonoxetane OXT-121", "Alonoxetane OXT-211", "Alonoxetane OXT-221" or "Alonoxetane OXT-212" manufactured by Toagosei Co., Ltd. can be used. These can be used alone or in combination of two or more.

[0057] According to one embodiment of the present invention, the content of the oxetane compound based on 100 parts by weight of the UV-curable ink composition may be 5 parts by weight or more and 25 parts by weight or less. Specifically, the content of the oxetane compound based on 100 parts by weight of the UV-curable ink composition may be 5 parts by weight or more and 23 parts by weight or less, 7 parts by weight or more and 25 parts by weight or less, 7 parts by weight or more and 23 parts by weight or less, 10 parts by weight or more and 25 parts by weight or less, 10 parts by weight or more and 23 parts by weight or less, 13 parts by weight or more and 25 parts by weight or less, 13 parts by weight or more and 23 parts by weight or less, 15 parts by weight or more and 25 parts by weight or less, 15 parts by weight or more and 23 parts by weight or less, or 15 parts by weight or more and 22 parts by weight or less. By adjusting the content of the oxetane compound contained in the UV-curable ink composition within the above range, the curing sensitivity, storage stability, and dispersibility of the UV-curable ink composition for forming a frame pattern can be improved. Furthermore, the hardness and adhesion of the photocured UV-curable ink composition used to form the frame pattern can be effectively improved. In particular, when the content of the oxetane compound is within the aforementioned range, a decrease in the curing sensitivity of the UV-curable ink composition used to form the frame pattern can be prevented, and a decrease in coating properties due to an increase in the viscosity of the UV-curable ink composition used to form the frame pattern can be effectively suppressed.

[0058] According to one embodiment of the present invention, the above-mentioned ultraviolet curable ink composition for forming a frame pattern may contain an epoxy compound. Specifically, the above-mentioned epoxy compound may contain an ester bond in the molecule. More specifically, the number of ester bonds contained in the molecule of the above-mentioned epoxy compound may be more than 1 and less than 4, more than 1 and less than 3, more than 1 and less than 2, or 1. By using an epoxy compound containing an ester bond within the above-mentioned range, the above-mentioned ultraviolet curable ink composition for forming a frame pattern having excellent curing sensitivity, storage stability and dispersibility can be achieved. In addition, the above-mentioned ultraviolet curable ink composition for forming a frame pattern may have excellent optical density, hardness and adhesion after curing.

[0059] According to one embodiment of the present invention, the epoxy compound may be an alicyclic epoxy compound. The alicyclic epoxy compound may contain an alicyclic epoxy group at the end. The “alicyclic epoxy group” may refer to an alicyclic ring group in which a cycloalkyl group having 5 to 10 carbon atoms is bonded to an epoxy group and two rings are fused and epoxidized. At this time, the hydrogen atoms constituting the cycloalkyl group may be arbitrarily substituted with substituents such as an alkyl group. For example, the alicyclic epoxy group may be 3,4-epoxycyclopentyl, 3,4-epoxycyclohexyl, 3,4-epoxycyclopentylmethyl, 3,4-epoxycyclohexylmethyl, 2-(3,4-epoxycyclopentyl)ethyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclopentyl)propyl or 3-(3,4-epoxycyclohexyl)propyl.

[0060] The alicyclic epoxy compound may contain one or more and four or one or more and two or fewer alicyclic epoxy groups. Using an epoxy compound containing alicyclic epoxy groups within the above range allows for the UV-curable ink composition for forming a frame pattern to exhibit excellent curing sensitivity, storage stability, and dispersibility. Furthermore, after curing, the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion.

[0061] According to one embodiment of the present invention, the alicyclic epoxy compound may include at least one of a first epoxy compound containing two alicyclic epoxy groups and a second epoxy compound containing one alicyclic epoxy group and one vinyl group. Specifically, the epoxy compound may include at least one of a compound represented by the following Chemical Formula 2-1 and a compound represented by the following Chemical Formula 2-2. More specifically, the alicyclic epoxy compound may be a compound represented by the following Chemical Formula 2-1.

[0062] [Chemical Formula 2-1]

[0063]

[0064] [Chemical Formula 2-2]

[0065]

[0066] In the above chemical formula 2-1, R 11 and R 13 may be each independently a single bond, or a linear or branched alkylene group having 1 to 5 carbon atoms, R 12 It can be a straight chain or branched alkylene group having 1 to 5 carbon atoms, and n3 can be 0 or an integer from 1 to 3. Specifically, R 11 and R 13Each independently may be a single bond, or a linear or branched alkylene group having 1 to 3 carbon atoms, or a linear or branched alkylene group having 1 to 2 carbon atoms. In addition, n3 may be 0 or an integer from 1 to 2, 1 or 0.

[0067] In the above chemical formula 2-2, R 14 It may be a single bond or a straight or branched chain alkylene group having 1 to 5 carbon atoms.

[0068] By using an alicyclic epoxy compound containing at least one of the compound represented by Chemical Formula 2-1 and the compound represented by Chemical Formula 2-2, the UV-curable ink composition for forming a frame pattern can be achieved with excellent curing sensitivity, storage stability, and dispersibility. Furthermore, the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion after curing.

[0069] In addition, more specifically, the compound represented by the above Chemical Formula 2-1 may be a compound represented by the following Chemical Formula 2-1a.

[0070] [Chemical Formula 2-1a]

[0071]

[0072] In the above chemical formula 2-1a, R 11 to R 13 and n3 may be the same as defined in the above chemical formula 2-1.

[0073] The alicyclic epoxy compound may include at least one of the following compounds 2-1 to 2-3. Specifically, the alicyclic epoxy compound may be the following compound 2-1 or compound 2-2.

[0074] [Compound 2-1]

[0075]

[0076] [Compound 2-2]

[0077]

[0078] [Compound 2-3]

[0079]

[0080] In addition, the alicyclic epoxy compound may include at least one of bisphenol epoxy compounds, novolac epoxy compounds, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, linear aliphatic epoxy compounds, biphenyl epoxy compounds, and alicyclic epoxy compounds.

[0081] For example, dicyclopentadiene dioxide can be used as the alicyclic epoxy compound. carbonyl chloride, 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)methanol, (3,4-epoxy-6-methylcyclohexyl)methyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene glycol bis(3,4-epoxycyclohexyl) ether, ethylene glycol diester of 3,4-epoxycyclohexenecarboxylate, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, or Celoxide 8000 from Daicel Corporation. These may be used alone or in combination of two or more.

[0082] According to one embodiment of the present invention, the content of the alicyclic epoxy compound can be from 10 parts by weight to 40 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the alicyclic epoxy compound can be from 12.5 parts by weight to 37.5 parts by weight, from 15 parts by weight to 35 parts by weight, from 13 parts by weight to 33 parts by weight, from 15 parts by weight to 40 parts by weight, from 20 parts by weight to 30 parts by weight, from 20 parts by weight to 25 parts by weight, or from 20 parts by weight to 22.5 parts by weight based on 100 parts by weight of the UV-curable ink composition. By adjusting the content of the alicyclic epoxy compound in the UV-curable ink composition to within the above range, the curing sensitivity, storage stability, and dispersibility of the UV-curable ink composition for forming a frame pattern can be improved. In addition, the optical density, hardness, and adhesion of the photocured product of the UV-curable ink composition for forming a frame pattern can be effectively improved. In particular, when the content of the alicyclic epoxy compound in the photocurable composition is within the above range, a decrease in the curing sensitivity of the ultraviolet curable ink composition for forming a frame pattern can be effectively prevented.

[0083] According to one embodiment of the present invention, the UV-curable ink composition may include a vinyl ether compound. Specifically, the vinyl ether compound may be a compound comprising a cycloalkylene group having 5 to 10 carbon atoms and a vinyl ether group bonded thereto. By utilizing such a vinyl ether compound having a cyclic alkyl backbone in its molecule, the UV-curable ink composition for forming a frame pattern can be achieved with excellent curing sensitivity, storage stability, and dispersibility. Furthermore, the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion after curing.

[0084] According to one embodiment of the present invention, the vinyl ether compound may contain at least one vinyl ether group. Specifically, the number of vinyl ether groups contained in the vinyl ether compound may be 1 to 3, 1 to 2, or 2. The vinyl ether compound may include a compound represented by the following Chemical Formula 3-1.

[0085] [Chemical Formula 3-1]

[0086]

[0087] In the above chemical formula 3-1, R 21 and R 22 may be each independently a single bond, or a linear or branched alkylene group having 1 to 5 carbon atoms, R 23 It can be a vinyl ether group or a hydroxyl group, n4 can be 0 or an integer from 1 to 2, and Cy1 can be a cycloalkylene group having 5 to 10 carbon atoms. Specifically, R 21 and R 22 Each of n4 and n5 may be independently a single bond, a linear or branched alkylene group having 1 to 3 carbon atoms, or a linear or branched alkylene group having 1 to 2 carbon atoms. n4 may be 0 or 1, and Cy1 may be a cycloalkylene group having 5 to 8 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or a cyclohexylene group.

[0088] By using a vinyl ether compound containing the compound represented by Chemical Formula 3-1, the UV-curable ink composition for forming a frame pattern can be achieved with excellent curing sensitivity, storage stability, and dispersibility. Furthermore, after curing, the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion.

[0089] In addition, more specifically, the compound represented by the above Chemical Formula 3-1 may be a compound represented by the following Chemical Formula 3-1a.

[0090] [Chemical Formula 3-1a]

[0091]

[0092] In the above chemical formula 3-1a, R 21 to R 23 It can be the same as defined in the above chemical formula 3-1, and n4 can be 0 or 1.

[0093] According to one embodiment of the present invention, the vinyl ether compound may include a first vinyl ether compound containing one vinyl ether end group or a second vinyl ether compound containing two or more vinyl ether end groups. Specifically, the second vinyl ether compound may contain 2 to 5, 2 to 3, or 2 vinyl ether end groups. By making the UV-curable ink composition contain the first vinyl ether compound or the second vinyl ether compound, the curing sensitivity, storage stability, and dispersibility of the UV-curable ink composition for forming the frame pattern can be improved. In addition, the optical density, hardness, and adhesion of the photocured material of the UV-curable ink composition for forming the frame pattern can be effectively improved. In particular, the curing sensitivity of the UV-curable ink composition for forming the frame pattern can be further improved.

[0094] According to one embodiment of the present invention, the vinyl ether compound may include at least one of the following compounds 3-1 to 3-3. Specifically, the vinyl ether compound may include the following compound 3-1.

[0095] [Compound 3-1]

[0096]

[0097] [Compound 3-2]

[0098]

[0099] [Compound 3-3]

[0100]

[0101] According to one embodiment of the present invention, the content of the vinyl ether compound based on 100 parts by weight of the UV-curable ink composition may be 10 parts by weight to 60 parts by weight. Specifically, the content of the vinyl ether compound based on 100 parts by weight of the UV-curable ink composition may be 10 parts by weight to 60 parts by weight, 10 parts by weight to 50 parts by weight, 10 parts by weight to 40 parts by weight, 10 parts by weight to 35 parts by weight, 20 parts by weight to 60 parts by weight, 20 parts by weight to 55 parts by weight, 20 parts by weight to 45 parts by weight, 20 parts by weight to 35 parts by weight, 25 parts by weight to 60 parts by weight, 25 parts by weight to 55 parts by weight, 25 parts by weight to 45 parts by weight, 25 parts by weight to 35 parts by weight, 26 parts by weight to 31 parts by weight, or 27 parts by weight to 31 parts by weight.

[0102] By adjusting the content of the vinyl ether compound in the UV-curable ink composition to within the above range, the curing sensitivity, storage stability, and dispersibility of the UV-curable ink composition for forming a frame pattern can be improved. Furthermore, the optical density, hardness, and adhesion of the photocured product of the UV-curable ink composition for forming a frame pattern can be effectively improved. In particular, the UV-curable ink composition for forming a frame pattern can be effectively prevented from curing poorly or experiencing a decrease in curing sensitivity under high humidity conditions.

[0103] According to one embodiment of the present invention, the UV-curable ink composition may include a diglycidyl ether compound. Examples of such diglycidyl ether compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-bis(2,3-epoxypropoxy)hexane, 4,4'-bis(2,3-epoxypropoxy)biphenyl, and 1,4-bis((2,3-epoxypropoxy)methyl)cyclohexane (CDMDG). These compounds may be used alone or in combination of two or more.

[0104] [Chemical Formula 4-1]

[0105]

[0106] [Chemical Formula 4-2]

[0107]

[0108] In the above Chemical Formula 4-1 and Chemical Formula 4-2, R 41 to R 46R and R are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and Cy2 is a cycloalkylene group having 5 to 10 carbon atoms. 41 to R 46 may be each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and Cy2 may be a cycloalkylene group having 5 to 8 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, or a cyclohexylene group.

[0109] According to one embodiment of the present invention, the diglycidyl ether compound may include the following compound 4-1 or compound 4-2.

[0110] [Compound 4-1]

[0111]

[0112] 1,4-Butanediol diglycidyl ether

[0113] CAS number: 2425-79-8

[0114] [Compound 4-2]

[0115]

[0116] 1,4-bis((2,3-epoxypropoxy)methyl)cyclohexane (CDMDG),

[0117] CAS number: 14228-73-0

[0118] According to one embodiment of the present invention, based on 100 parts by weight of the above-mentioned ultraviolet curable ink composition, the content of the above-mentioned diglycidyl ether compound can be greater than 2.5 parts by weight and less than 10 parts by weight, greater than 3 parts by weight and less than 10 parts by weight, greater than 4 parts by weight and less than 10 parts by weight, or greater than 5 parts by weight and less than 10 parts by weight.

[0119] By adjusting the content of the diglycidyl ether compound contained in the photocurable composition within the above range, the curing sensitivity of the UV-curable ink composition for forming a frame pattern under atmospheric conditions can be improved, and a solvent-free UV-curable ink composition for forming a frame pattern with excellent properties can be ensured without problems such as thickness reduction and adhesion reduction under high temperature and high humidity conditions.

[0120] According to one embodiment of the present invention, the ultraviolet curable ink composition for forming a frame pattern includes a cationic initiator and a free radical initiator as photoinitiators. The cationic initiator is a cationic photopolymerization initiator and can be a compound that generates a cationic species or a Bronsted acid by irradiation with light (e.g., ultraviolet light). The cationic initiator can include a sulfonate having an asymmetric structure. Specifically, the cationic initiator can include a phenylsulfonate having two sulfur (S) atoms in its molecule and an asymmetric structure. For example, the cationic initiator can include the following compound 5-1.

[0121] [Compound 5-1]

[0122]

[0123] By using a cationic initiator containing a sulfonate with an asymmetric structure, the curing sensitivity, storage stability, and dispersibility of the UV-curable ink composition for forming a frame pattern can be improved, and the UV-curable ink composition for forming a frame pattern can exhibit excellent optical density, hardness, and adhesion after curing. If the cationic initiator is a sulfonate with a symmetrical structure, or a sulfonate or iodine salt containing one sulfur atom, one sulfur atom, or three or more sulfur atoms in the molecule, the curing sensitivity and storage stability of the UV-curable ink composition for forming a frame pattern may be reduced, and the physical properties of the photocured product of the UV-curable ink composition for forming a frame pattern, such as hardness, adhesion, and optical density, may also be deteriorated.

[0124] According to one embodiment of the present invention, the content of the cationic initiator can be from 2 parts by weight to 6 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the cationic initiator can be from 3 parts by weight to 6 parts by weight, from 3 parts by weight to 5 parts by weight, from 3 parts by weight to 4 parts by weight, from 4 parts by weight to 5 parts by weight, from 3.5 parts by weight to 5.5 parts by weight, or from 4 parts by weight to 6 parts by weight based on 100 parts by weight of the UV-curable ink composition. When the content of the cationic initiator is within the above range, the photocuring reaction of the UV-curable ink composition for forming a frame pattern can proceed stably, and precipitation of the initiator in the UV-curable ink composition for forming a frame pattern, which could lead to reduced stability, can be prevented. The formation of cationic initiator precipitation in the UV-curable ink composition for forming a frame pattern can be suppressed, and the viscosity of the UV-curable ink composition for forming a frame pattern, which could lead to reduced coating properties, can be prevented.

[0125] According to one embodiment of the present invention, the UV-curable ink composition for forming a frame pattern may include a free radical initiator. The free radical initiator may be a free radical photopolymerization initiator. The free radical initiator acts as a co-initiator to supplement the insufficient reactivity of the cationic initiator.

[0126] According to one embodiment of the present invention, the content of the free radical initiator may be from 1 part by weight to 4 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the free radical initiator may be from 1 part by weight to 3.5 parts by weight, or from 1 part by weight to 3 parts by weight based on 100 parts by weight of the UV-curable ink composition.

[0127] In addition to the cationic initiator, the above-mentioned free radical initiator also plays a role in initiating and enhancing the polymerization of the above-mentioned monomers. If the content of the above-mentioned free radical initiator is lower than the above-mentioned range based on 100 parts by weight of the above-mentioned UV-curable ink composition, its reactivity is insufficient. If its content exceeds the above-mentioned range, although the reactivity is enhanced, it may lead to a decrease in properties such as adhesion and solubility problems.

[0128] As the free radical initiator, it is preferred to use at least one of an acylphosphine photoinitiator, a diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide photoinitiator, an acetylphenone photoinitiator, and an α-hydroxyketone photoinitiator. Specific examples of the free radical initiator include diacetyl, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, and benzoinisopropyl ether. ether), acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-methylethyl-phenyl ketone, p-isopropyl-α-hydroxyisobutylphenyl ketone, N,N-dimethylaminoacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone, ethyl p-dimethylaminobenzoate, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-dimethoxy-1-phenyl ... Methylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl acetal, benzyl dimethyl acetal, benzophenone, methyl benzophenone, trimethylbenzophenone (TZT), 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-dichlorobenzophenone, diethylthioxanthone (DETX), 2-isopropylthioxanthone (ITX), 4,4'-bis(diethylamino)benzophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone (IRGACURE907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (IRGACURE 369), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butanone (IRGACURE 379), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(η 5-2,4-cyclopentadien-1-yl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methylpropionyl)phenyl]-1,3,3-trimethylinden-5-yl}-2-methylpropanone (ESACURE ONE), 1-propanone, 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl] (ESACURE 1001M), bis-N,N-[(4-dimethylaminobenzoyl)oxyethylen-lyl]-methylamine, or a mixture of two or more thereof. The above-mentioned free radical initiator may include the following compound 5-2.

[0129] [Compound 5-2]

[0130]

[0131] 2-Hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, CAS No.: 474510-57-1 (Omnirad 127D)

[0132] According to one embodiment of the present invention, the weight ratio of the free radical initiator to the cationic initiator can be 1:1 to 1:6. Specifically, the weight ratio of the free radical initiator to the cationic initiator can be 1:1 to 1:6, 1:1 to 1:5, 1:1 to 1:4, 1:1 to 1:3, or 1:3 to 1:4. When the weight ratio of the free radical initiator to the cationic initiator contained in the ultraviolet curable ink composition is within the above range, the photocuring reaction of the ultraviolet curable ink composition for forming a frame pattern can be stably carried out, and the precipitation of the initiator in the ultraviolet curable ink composition for forming a frame pattern, which leads to a decrease in stability, can be prevented. The generation of precipitates of the cationic initiator in the ultraviolet curable ink composition for forming a frame pattern can be suppressed, and the viscosity of the ultraviolet curable ink composition for forming a frame pattern can be prevented from increasing, which leads to a decrease in coating properties.

[0133] On the other hand, when the weight ratio of the radical initiator to the cationic initiator in the UV-curable ink composition exceeds the above range, insufficient reactivity may result, or excessive reactivity may result in decreased adhesion and other performance issues and solubility problems.

[0134] According to one embodiment of the present invention, the UV curable ink composition for forming a frame pattern may further include additives. Specifically, the additives may include at least one of a sensitizer, an adhesion enhancer, a surfactant, and an antioxidant.

[0135] According to one embodiment of the present invention, the ultraviolet curable ink composition for forming a frame pattern may contain a sensitizer as an additive. As the sensitizer, any sensitizer used in the art can be used. For example, the sensitizer can be an anthracene compound selected from anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, etc.; a benzophenone compound such as benzophenone, 4,4-bis(dimethylamino)benzophenone, 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl-o-benzoylbenzoic acid ethyl ester, 3,3-dimethyl-4-methoxybenzophenone, 3,3,4,4-tetra(tert-butylperoxycarbonyl)benzophenone, etc.; an acetone compound such as acetophenone, dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, acetone, etc. perylene; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone; thioxanthene compounds such as thioxanthene, 2,4-diethylthioxanthene, 2-chlorothioxanthene, 1-chloro-4-propoxythioxanthene, isopropylthioxanthene (ITX), diisopropylthioxanthene; xanthone compounds such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone, 2,6-dichloro-9,10-anthraquinone; acridine compounds such as 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, 1,3-bis(9-acridinyl)propane; benzyl, 1,7,7-trimethylolpropane dicarbonyl compounds such as 2,3-dione, 9,10-phenanthrenequinone, etc.; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc.; benzoate compounds such as methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, etc.; amino compounds such as 2,5-bis(4-diethylaminophenylylidene)cyclopentanone, 2,6-bis(4-diethylaminophenylylidene)cyclohexanone, 2,6-bis(4-diethylaminophenylylidene)-4-methylcyclopentanone, etc. Sensitizers; at least one of the group consisting of coumarin compounds such as 3,3-carbonylvinylene-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3-benzoyl-7-methoxycoumarin, 10,10-carbonylbis[1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-C1]benzopyrano[6,7,8-ij]quinolin-11-one, etc.; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzylideneacetophenone, etc.; 2-benzoylmethylene; and compounds such as 3-methyl-β-naphthothiazoline.

[0136] According to one embodiment of the present invention, the content of the sensitizer can be from 1 part by weight to 4.5 parts by weight based on 100 parts by weight of the UV-curable ink composition. Specifically, the content of the sensitizer can be from 1 part by weight to 4 parts by weight, from 1 part by weight to 3 parts by weight, or from 2 parts by weight to 3 parts by weight based on 100 parts by weight of the UV-curable ink composition. By adjusting the content of the sensitizer within the above range, a decrease in curing sensitivity can be prevented, thereby improving the coating properties of the photocured product of the UV-curable ink composition for forming a frame pattern. In addition, the sensitizer can be prevented from precipitating in the UV-curable ink composition for forming a frame pattern, thereby preventing a decrease in stability.

[0137] According to one embodiment of the present invention, the UV-curable ink composition for forming a frame pattern may include a surfactant as an additive. The addition of a surfactant can reduce the surface tension of the UV-curable ink composition for forming a frame pattern, thereby improving the coating properties of the UV-curable ink composition for forming a frame pattern. The surfactant can be any surfactant commonly used in the art. For example, as the surfactant, one may use one selected from Megaface F444, F-475, F-478, F-479, F-484, F-550, F-552, F-553, F-555, F-570, and RS-75 of DIC (Dainippon Ink & Chemicals); Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 of Asahi Glass Co., Ltd.; Fluorad FC93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, and FC-4430 of SUMITOMO 3M; Zonyl FS-300, FSN, FSN-100 and FSO; and BYK's BYK-306, BYK-310, BYK-320, BYK-330, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-355, BYK-356, BYK-3 58N, 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 a surfactant from the group consisting of Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370 and Flow 425 from TEGO.

[0138] According to one embodiment of the present invention, the content of the surfactant can be 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, 0.1 to 1 part by weight, 0.2 to 5 parts by weight, 0.2 to 3 parts by weight, 0.2 to 1 part by weight, or 0.2 to 0.5 parts by weight, based on 100 parts by weight of the UV-curable ink composition. By adjusting the content of the surfactant within the above range, the surface tension of the UV-curable ink composition for forming a frame pattern can be effectively reduced, thereby effectively applying the UV-curable ink composition for forming a frame pattern to a substrate. In addition, the compatibility and defoaming properties of the UV-curable ink composition for forming a frame pattern can be prevented from being reduced.

[0139] According to one embodiment of the present invention, the ultraviolet curable ink composition for forming a frame pattern may include an adhesion enhancer as an additive. By adding an adhesion enhancer, the light-cured material of the ultraviolet curable ink composition for forming a frame pattern can be effectively prevented from peeling off from the substrate. Examples of the adhesion enhancer may include a silane compound. The silane compound that can be used as the adhesion enhancer may include, for example, one of an alkoxysilane compound, an epoxysilane compound, an aminophenylsilane compound, an aminosilane compound, a mercaptosilane compound, and a vinylsilane compound. Specifically, the adhesion enhancer may include at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-methacryloxypropyltrimethoxysilane. However, the type of the adhesion enhancer is not limited, and the adhesion enhancer may also include a phosphate-based acrylate compound.

[0140] According to one embodiment of the present invention, the content of the adhesion enhancer can be from 1 to 10 parts by weight, from 3 to 7 parts by weight, or from 5 to 7 parts by weight, based on 100 parts by weight of the UV-curable ink composition. When the content of the adhesion enhancer is within this range, the photocured material of the UV-curable ink composition for forming a frame pattern can be effectively prevented from peeling off from the substrate. Furthermore, the viscosity increase and dispersibility decrease of the UV-curable ink composition for forming a frame pattern can be suppressed.

[0141] According to one embodiment of the present invention, the ultraviolet curable ink composition for forming a frame pattern may contain an antioxidant as an additive. As the above-mentioned antioxidant, antioxidants commonly used in the art can be used without restriction. Based on 100 parts by weight of the above-mentioned ultraviolet curable ink composition, the content of the above-mentioned antioxidant can be 0.01 parts by weight or more and 0.2 parts by weight or less, 0.01 parts by weight or more and 0.1 parts by weight or less, 0.01 parts by weight or more and 0.07 parts by weight or less, 0.03 parts by weight or more and 0.07 parts by weight or less, or 0.05 parts by weight or more and 0.1 parts by weight or less. By adjusting the content of the antioxidant to within the above-mentioned range, the photocured material of the ultraviolet curable ink composition for forming a frame pattern can be effectively prevented from being oxidized, thereby further improving long-term reliability.

[0142] On the other hand, the types of additives contained in the ultraviolet curable ink composition for forming a frame pattern are not limited to the above-mentioned types, and other additives used in the art may be contained within a range that does not impair the required performance.

[0143] According to one embodiment of the present invention, the UV-curable ink composition for forming a frame pattern may have a viscosity of 3 cP to 30 cP at 25°C. Specifically, the viscosity of the UV-curable ink composition for forming a frame pattern at 25°C may be 3 cP to 25 cP, 3 cP to 20 cP, 5 cP to 25 cP, 5 cP to 20 cP, 10 cP to 30 cP, 10 cP to 20 cP, 14 cP to 30 cP, 14 cP to 25 cP, or 14 cP to 20 cP. A UV-curable ink composition for forming a frame pattern having a viscosity within the above range can exhibit excellent coating properties, inkjet ejection properties, and processability. Specifically, when the viscosity of the UV-curable ink composition for forming a frame pattern is within the above range, it is suitable for inkjet processing and exhibits good ejection at process temperatures. The process temperature is a temperature at which the viscosity of the ultraviolet curable ink composition for forming a frame pattern is reduced by heating, and may be 10° C. to 100° C., or 20° C. to 70° C.

[0144] According to one embodiment of the present invention, the UV-curable ink composition for forming a frame pattern can be an ink for forming a black pattern. By having the above-mentioned composition, the UV-curable ink composition for forming a frame pattern has good coating properties when forming a black pattern, and after photocuring, it can have excellent light-shielding properties even at a very thin thickness. Furthermore, the UV-curable ink composition for forming a frame pattern has excellent curing sensitivity, so it can easily form a black pattern through UV curing under atmospheric conditions without external stabilization conditions such as nitrogen filling. It can also effectively suppress the formation of wrinkles on the surface of the formed black pattern, thereby achieving a high-quality black pattern.

[0145] One embodiment of the present invention provides a black pattern including a cured product of the above-mentioned ultraviolet curable ink composition for forming a frame pattern.

[0146] The black pattern can be formed using the UV-curable ink composition for forming a frame pattern by a method known in the art. For example, the black pattern can be formed using the UV-curable ink composition for forming a frame pattern by a method comprising inkjet printing the UV-curable ink composition for forming a frame pattern to form a black pattern on a substrate, and curing the black pattern by ultraviolet irradiation.

[0147] According to one embodiment of the present invention, the UV-curable ink composition for forming a frame pattern can be spread in a short time immediately after inkjet printing, exhibiting excellent coating properties, and can be cured to exhibit excellent adhesive properties. Therefore, when the black pattern is formed using the UV-curable ink composition for forming a frame pattern, a light source (e.g., a UV lamp) is preferably provided directly behind the inkjet head so that inkjet printing and curing can be achieved simultaneously.

[0148] According to one embodiment of the present invention, in order to photocure the ultraviolet curable ink composition for forming a frame pattern, 500 mJ / mm 2 Above and 5,000mJ / mm 2 The total exposure dose is 500 mJ / mm 2 Above and 5,000mJ / mm 2 Below, 500mJ / mm 2 Above and 4,000mJ / mm 2 Below, 500mJ / mm 2 Above and 3,000mJ / mm 2 Below, 1,000mJ / mm 2Above and 5,000mJ / mm 2 Below, 1,000mJ / mm 2 Above and 4,000mJ / mm 2 Below, 1,000mJ / mm 2 Above and 3,000mJ / mm 2 Below or 2,000mJ / mm 2 Above and 3,000mJ / mm 2 The light having a wavelength range of 360 nm to 410 nm was irradiated with the following total exposure amount to photocure the ultraviolet curable ink composition for forming the frame pattern.

[0149] According to one embodiment of the present invention, the black pattern of the photocurable material including the above-mentioned ultraviolet-curable ink composition for forming a border pattern can show a pencil hardness of 1B or more in the pencil hardness test result. Specifically, the above-mentioned black pattern can show a pencil hardness of 1H or more or F or more. In addition, the black pattern of the photocurable material including the above-mentioned ultraviolet-curable ink composition for forming a border pattern can show an adhesion of 4B or more in the cross-cutting test result (the area dropped is less than 5% of the total area). That is, the black pattern of the photocurable material including the above-mentioned ultraviolet-curable ink composition for forming a border pattern can have excellent hardness and adhesion (adhesion) to the substrate. In addition, the black pattern of the photocurable material including the above-mentioned ultraviolet-curable ink composition for forming a border pattern can have a thickness change rate of less than 5% during the heat resistance evaluation and reliability evaluation.

[0150] One embodiment of the present invention provides a display substrate including the aforementioned black pattern. As described above, the black pattern, which includes a photocured product of the UV-curable ink composition for forming a frame pattern, can exhibit excellent surface quality and adhesion to the substrate, and has excellent optical density even at a relatively thin thickness. Therefore, the display substrate including the black pattern can have excellent quality. Therefore, by using the aforementioned display substrate, a display device with excellent image quality can be realized.

[0151] Modes for carrying out the invention

[0152] The present invention will be described in detail below with reference to the embodiments. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments to be described below. The embodiments of this specification are provided so that those skilled in the art can more completely understand the present invention.

[0153] Compound

[0154] 1) Black pigment: CB-22

[0155] 2) Dispersant:

[0156] - Polyurethane type: Disperbyk 160 (manufactured by BYK)

[0157] 3) Oxetane compounds:

[0158] -Compound 1-1 (bis[1-ethyl(3-oxetanyl)]methyl ether; OXT-221; manufactured by Toagosei Co., Ltd.)

[0159] 4) Alicyclic epoxy compounds:

[0160] -Compound 2-1 ((3',4'-epoxycyclohexane)methyl-3,4-epoxycyclohexylcarboxylate; Celloxide 2021P; manufactured by Daicel Corporation)

[0161] 5) Vinyl ether compounds:

[0162] -Compound 3-1 (cyclohexyl vinyl ether; CHVE; manufactured by BASF Corporation)

[0163] 6) Diglycidyl ether compounds:

[0164] -Compound 4-2 (1,4-cyclohexanedimethanol diglycidyl ether; CDMDG; manufactured by Showa Denko K.K.)

[0165] 6) Photoinitiator (cationic initiator):

[0166] -Compound 5-1 (4-(Phenylthio)phenyldiphenylsulfonium tris(pentafluoroethyl)trifluorophosphate; CPI-210S; manufactured by San-Apro)

[0167] 7) Sensitizer:

[0168] -UVS-1331 (9,10-dibutoxyanthracene; manufactured by Kawasaki Heavy Industries, Ltd.)

[0169] 8) Free radical initiator (coinitiator):

[0170] -Compound 5-2Omnirad 127D (2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-2-methylpropan-1-one; manufactured by IGM Resins)

[0171] 9) Adhesion enhancer: KBM-403 (3-glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu Chemical Co., Ltd.)

[0172] 10) Surfactant: F-554 (manufactured by DIC Corporation)

[0173] 11) Antioxidant: BHT (manufactured by Junsei Chemical Co., Ltd.)

[0174] Example

[0175] Example 1

[0176] Preparation of high heat-resistant ultraviolet curable ink composition for forming frame pattern

[0177] CB-22 as a black pigment, polyurethane-type Disperbyk160 as a dispersant, compound OXT-221 as an oxetane compound, compound 2021P as an alicyclic epoxy compound, CHVE as a vinyl ether compound, compound CDMDG as a diglycidyl ether compound, CPI-210S as a photoinitiator (cationic initiator), UVS-1331 as a sensitizer, Omnirad127D as a co-initiator (free radical photoinitiator), KBM-403 as an adhesion enhancer, F-554 as a surfactant, and BHT as an antioxidant were stirred at room temperature for 6 hours to prepare a UV-curable ink composition for forming a frame pattern.

[0178] At this time, based on 100 parts by weight of the photocurable composition, the content of the black pigment is 11 parts by weight, the content of the dispersant is 2.75 parts by weight, the content of the oxetane compound is 15 parts by weight, the content of the alicyclic epoxy compound is 21 parts by weight, the content of the vinyl ether compound is 31 parts by weight, the content of the diglycidyl ether compound is 5 parts by weight, the content of the photoinitiator (cationic initiator) is 4 parts by weight, the content of the co-initiator (free radical photoinitiator) is 1 part by weight, the content of the sensitizer is 3 parts by weight, the content of the adhesion enhancer is 6 parts by weight, the content of the surfactant is 0.2 parts by weight, and the content of the antioxidant is 0.05 parts by weight.

[0179] Example 2 to Example 5

[0180] Except for adjusting the composition as shown in Table 1, an ultraviolet curable ink composition for forming a frame pattern was prepared in the same manner as in Example 1.

[0181] Table 1

[0182]

[0183] Comparative Examples 1 to 6

[0184] Except for adjusting the composition as shown in Table 2, an ultraviolet curable ink composition for forming a frame pattern was prepared in the same manner as in Example 1.

[0185] Table 2

[0186]

[0187] The contents (parts by weight) of the components described in Tables 1 and 2 are based on 100 parts by weight of the ultraviolet curable ink composition for forming a frame pattern.

[0188] Experimental example

[0189] Viscosity measurement

[0190] The viscosity of the UV-curable ink composition for forming a frame pattern prepared in Example 1 was measured at room temperature (25°C) using a Brookfield viscometer with a conical spindle (CPA-40Z). The results are reported in Table 3 below.

[0191] The viscosities of the UV-curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also measured in the same manner, and the results are shown in Table 3 below.

[0192] The viscosities of the UV-curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also measured in the same manner, and the results are shown in Table 4 below.

[0193] Curing sensitivity evaluation

[0194] The UV curable ink composition for forming a frame pattern prepared in Example 1 was applied to a glass substrate (5×5 cm) using a dropper and spin-coated at a rotation speed of about 3,000 rpm to a film thickness of 3 μm. Subsequently, a UV irradiation device (395 nm UV LED) was used to irradiate the glass substrate with a total exposure dose of 2000 mJ / cm 2 The UV curable ink composition used to form the frame pattern is cured by applying UV light. The exposure amount is measured and calculated using an illuminometer.

[0195] One minute after UV irradiation, the UV-curable ink composition used to form the frame pattern was lightly touched with a finger. If the film was not completely cured and the liquid was stained on the hand, it was judged as uncured and marked as "poor." If the film was not completely cured and still had tack (tack), it was marked as "poor." If the film was completely cured and had no tack, it was marked as "good." The results are reported in Table 3 below.

[0196] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0197] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0198] Storage stability evaluation

[0199] The storage stability of the ultraviolet curable ink composition for forming a frame pattern obtained in the above-mentioned Example 1 was measured. Specifically, about 15 ml of the composition was injected into a 20 ml brown glass bottle, and then its storage stability at low temperature (7°C) and normal temperature (25°C) was evaluated. The viscosity of the composition in each container was measured at 25°C using a viscometer DV-2 (Brookfield). After being placed at low temperature (7°C) and normal temperature (25°C) for one month, when the viscosity change rate of the composition {(viscosity value after change / initial viscosity value-1)} reached or exceeded 50%, it was evaluated as ×, between 10% and 50%, it was evaluated as △, and below 10%, it was evaluated as ○, and the results are shown in Table 3 below.

[0200] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0201] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0202] Pencil hardness evaluation

[0203] The UV-curable ink composition for forming a frame pattern prepared in Example 1 was cured using the same method as described in the "Evaluation of Curing Sensitivity" section above to prepare a black sample. Subsequently, a pencil hardness tester was used to measure the hardness of the sample, applying a load of 200 gf using three strokes with each pencil. The degree of scratching and indentation was measured according to JIS K5400. The results are reported in Table 3 below.

[0204] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0205] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0206] For reference, the pencil hardness rating from low to high is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H.

[0207] Adhesion evaluation

[0208] The ultraviolet curable ink composition for forming a frame pattern obtained in Example 1 was cured in the same manner as in the above-mentioned "Evaluation of Curing Sensitivity" to prepare a black sample. The prepared black sample was subjected to a cross-cut test in accordance with ASTM D3359, which is a cross-cutting standard. Specifically, a cutter was used to carve 10 lines vertically and horizontally on the surface of the sample at intervals of 1 mm, forming a total of 100 1 mm × 1 mm squares. Afterwards, CT-24 tape produced by Nichiban Co., Ltd. was attached to the above-mentioned cut section and torn off, and the condition of the surface that fell together was observed using an optical microscope.

[0209] -Cross-cut Adhesion Evaluation Standard-

[0210] 5B: The surface area of the drop remains unchanged compared to the initial state

[0211] 4B: The surface area of the drop is less than 5% of the total area

[0212] 3B: The surface area of the drop is 5% or more but less than 15% of the total area

[0213] 2B: The surface area of the drop is 15% or more but less than 35% of the total area

[0214] 1B: The surface area of the drop is 35% or more, but less than 65% of the total area

[0215] 0B: The surface area of the drop accounts for 65% or more, but less than 100% of the total area

[0216] X: Black sample not attached (dropped surface accounts for 100% of the total area)

[0217] The results of testing Examples 1 to 5 according to the above evaluation criteria are recorded in Table 3 below, and the results of testing Comparative Examples 1 to 6 according to the above criteria are recorded in Table 4 below.

[0218] Evaluation of solubility and precipitation

[0219] When preparing the UV-curable ink composition for forming a frame pattern, as prepared in Example 1, the solubility of the photoinitiator and sensitizer was evaluated. The results are shown in Table 3 below. Specifically, if no precipitate was observed with the naked eye, the evaluation was ○; if a small amount of precipitate was formed or it was difficult to detect with the naked eye, the evaluation was △; if a large amount of precipitate was formed, the evaluation was X.

[0220] Separately, a black sample was prepared by curing the UV-curable ink composition for forming a frame pattern, prepared in Example 1, using the same method as described in the "Cure Sensitivity Evaluation" section. The prepared black sample was examined and evaluated using an optical microscope to determine if any surface protrusions, such as those caused by precipitation, were present. If the sample was good, with no precipitation (protrusions, pits, etc.), it was marked with a ◯; if precipitation (protrusions, pits, etc.) was present, it was marked with an X.

[0221] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0222] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0223] Optical density / thickness (OD / μm) evaluation of black film

[0224] The UV-curable ink composition for forming a frame pattern, prepared in Example 1, was cured using the same method as described in the "Cure Sensitivity Evaluation" section above to prepare a black sample. The optical density of the black sample was then measured using an X-rite OD meter, and the thickness of the black sample was measured at the same location as the optical density (OD) measurement using an Alpha-step thickness meter. The measured data were then used to calculate OD / μm, which is shown in Table 3 below.

[0225] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0226] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0227] Thickness change rate evaluation (heat resistance evaluation)

[0228] The UV-curable ink composition for forming a frame pattern, prepared in Example 1, was cured using the same method as described in the "Cure Sensitivity Evaluation" section above to prepare a black sample. The thickness of the black sample was then measured using an Alpha-step thickness gauge. After placing the sample on a hot plate at 85°C for 30 minutes, the thickness of the same portion was measured. A black sample with a thickness change (post-change thickness / initial thickness) of 10% or greater was evaluated as ×, a black sample with a thickness change of 10% to 5% was evaluated as △, and a black sample with a thickness change of less than 5% was evaluated as ○. The results are shown in Table 3 below.

[0229] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0230] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0231] Reliability evaluation

[0232] The ultraviolet curable ink composition for forming a frame pattern obtained in Example 1 was cured in the same manner as in the above-mentioned "Evaluation of Curing Sensitivity" to prepare a black sample. Subsequently, the black sample was placed under 85 / 85 conditions (85°C temperature and 85% relative humidity) for 200 hours, and the adhesion of the black sample was measured using the same method as in the above-mentioned "Evaluation of Adhesion". In addition, the thickness was measured using Alpha-step. If the thickness change rate of the black sample (thickness after change / initial thickness) is 10% or more, it is evaluated as ×, if it is 10% to 5%, it is evaluated as △, and if it is less than 5%, it is evaluated as ○, and the results are shown in Table 3 below.

[0233] The UV curable ink compositions for forming frame patterns prepared in Examples 2 to 5 were also evaluated in the same manner, and the results are shown in Table 3 below.

[0234] The UV curable ink compositions for forming frame patterns prepared in Comparative Examples 1 to 6 were also evaluated in the same manner, and the results are shown in Table 4 below.

[0235] Table 3

[0236]

[0237] Table 4

[0238]

[0239] As can be seen from Table 3 above, in Examples 1 to 5 of the present invention, the UV-curable ink compositions used to form the frame pattern have suitable viscosity in the inkjet process and exhibit excellent performance in evaluations such as curing sensitivity, storage stability, pencil hardness, adhesion, solubility, optical density / thickness, and thickness change rate caused by heat.

[0240] On the other hand, referring to Table 4, in the case of Comparative Example 1, it was confirmed that it was difficult to ensure adhesion and heat resistance in the composition containing no diglycidyl ether compound.

[0241] Specifically, when evaluating heat resistance, the thickness after evaluation was significantly reduced compared to the initial thickness, indicating that it was difficult for Comparative Example 1 to ensure good heat resistance.

[0242] In Comparative Example 2, it was confirmed that when the diglycidyl ether compound reaches or exceeds a certain ratio in the composition of the photocurable composition, it will lead to an increase in viscosity and a decrease in surface curing sensitivity. Specifically, when the diglycidyl ether compound reaches or exceeds a certain ratio in the composition of the photocurable composition, residual monomers that do not participate in the curing reaction after crosslinking will cause the surface film layer after curing to become soft, thereby reducing the curing sensitivity.

[0243] In Comparative Example 3, the photocurable composition did not contain a free radical initiator, resulting in reduced curing sensitivity and poor hardness. Specifically, residual monomers in the photocurable composition that did not participate in the curing reaction softened the surface film after curing, thereby causing a decrease in hardness.

[0244] In the case of Comparative Example 4, when the content of the radical initiator in the composition of the photocurable composition reached or exceeded a certain ratio, solubility problems occurred, resulting in curing characteristics being so poor that they could hardly be evaluated.

[0245] In the case of Comparative Example 5, when the content of the oxetane compound in the composition of the photocurable composition reached or exceeded a certain ratio, the viscosity increased and the adhesion evaluation result was extremely poor.

[0246] In the case of Comparative Example 6, when the content of the cationic initiator in the composition of the photocurable composition reached or exceeded a certain ratio, solubility problems occurred, resulting in properties being so poor that they could hardly be evaluated.

[0247] In summary, the highly heat-resistant UV-curable ink composition for forming a frame pattern according to one embodiment of the present invention has excellent curing sensitivity, and can be easily photocured even under atmospheric conditions without external stabilization conditions such as nitrogen filling. At the same time, it has good storage stability and dispersibility, and the photocured product of the UV-curable ink composition for forming a frame pattern exhibits excellent optical density, hardness, adhesion, and other aspects.

[0248] The above detailed description is intended to illustrate the present invention. Furthermore, the foregoing description is intended only to illustrate preferred embodiments of the present invention. As previously mentioned, the present invention may be applied in a variety of other combinations, modifications, and environments, and may be modified or amended within the scope of the inventive concept disclosed in this specification, the scope of equivalents of the above disclosure, and / or the skill or knowledge of those skilled in the art. Therefore, the above detailed description of the present invention is not intended to limit the present invention to the disclosed embodiments. Furthermore, the appended claims should be interpreted as encompassing other embodiments.

Claims

1. A UV curable ink composition for forming a frame pattern, characterized in that: The invention comprises a pigment, a dispersant, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, a diglycidyl ether compound, a cationic initiator and a free radical initiator.

2. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The pigment includes a black pigment, and the content of the pigment is 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

3. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The above-mentioned dispersants include polyurethane compounds.

4. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The content of the dispersant is 1 part by weight or more and 6 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

5. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The content of the oxetane compound is 5 parts by weight or more and 25 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

6. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The alicyclic epoxy compound may be present in an amount of 10 parts by weight to 40 parts by weight based on 100 parts by weight of the ultraviolet curable composition.

7. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The content of the vinyl ether compound is 10 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

8. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The diglycidyl ether compound may be present in an amount of 2.5 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

9. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The content of the cationic initiator is 2 parts by weight or more and 6 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

10. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The content of the radical initiator is 1 part by weight or more and 4 parts by weight or less based on 100 parts by weight of the ultraviolet curable composition.

11. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The weight ratio of the free radical initiator to the cationic initiator is 1:1 to 1:

6.

12. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The invention further comprises an additive comprising at least one of a sensitizer, an adhesion enhancer, a surfactant and an antioxidant.

13. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein When the photocured product of the ultraviolet curable ink composition for forming a frame pattern was subjected to reliability evaluation, the thickness change rate was less than 5%, and the adhesion was 4B or greater.

14. The ultraviolet curable ink composition for forming a frame pattern according to claim 1, wherein The above-mentioned ultraviolet curable ink composition for forming a frame pattern is an ultraviolet curable ink composition for forming a black pattern.

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