WO2019117581A1 - Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same - Google Patents

Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same Download PDF

Info

Publication number
WO2019117581A1
WO2019117581A1 PCT/KR2018/015664 KR2018015664W WO2019117581A1 WO 2019117581 A1 WO2019117581 A1 WO 2019117581A1 KR 2018015664 W KR2018015664 W KR 2018015664W WO 2019117581 A1 WO2019117581 A1 WO 2019117581A1
Authority
WO
WIPO (PCT)
Prior art keywords
ink composition
weight
ultraviolet curable
bezel pattern
curable ink
Prior art date
Application number
PCT/KR2018/015664
Other languages
French (fr)
Korean (ko)
Inventor
유재현
박성은
김아름
김준형
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180157794A external-priority patent/KR102260090B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880015062.6A priority Critical patent/CN110382640B/en
Priority to US16/492,811 priority patent/US10858525B2/en
Priority to JP2019546930A priority patent/JP6911274B2/en
Publication of WO2019117581A1 publication Critical patent/WO2019117581A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the present invention relates to a UV curable black ink composition for a foldable display, a method of forming a bezel pattern using the same, a bezel pattern manufactured thereby, and a display substrate comprising the same.
  • Foldable display like other display devices, has a bezel pattern Is required.
  • the bezel In order to prevent the panel pattern from being visually recognized due to the nature of the mobile device, the bezel should have a high light shielding property. However, when the bezel becomes thick, the bezel step is visually recognized on the screen.
  • a bezel pattern having a thin thickness and excellent light shielding property is required, and an ink composition capable of suppressing surface wrinkling is required in order to UV cure the high light-shielding black ink by single layer printing.
  • Korean Patent Laid-Open Publication No. 10-2016-0147535 has developed an ultraviolet curable black ink capable of forming a bezel by an inkjet process. However, it has a light shielding property (optical density (OD) 1@2.2 ⁇ m) It is difficult to apply it to the folder blind due to the problem of visibility of the panel pattern.
  • Korean Patent Laid-Open Publication No. 10-2016-0046723 has developed an ink having a high light-shielding property by printing at 1 degree, but a heat treatment process is applied before UV curing to suppress surface wrinkles.
  • the inks disclosed in the above prior art documents are difficult to apply to a foldable cover window film with bezel ink developed for application to glass substrates.
  • a black bezel ink for application to a cover window film of a foldable display which has excellent light shielding property and folding property at a thin thickness, and which does not cause surface wrinkling caused by difference in curing rate between the bezel upper and lower bezel only by UV curing Development is required.
  • the present invention provides a method of forming an ultraviolet curable black ink composition which does not cause surface wrinkles caused by a difference in curing rate between the upper and lower portions, a method of forming a bezel pattern using the same, a bezel pattern manufactured thereby, and a display substrate comprising the same.
  • the present invention provides a black pigment, Dispersing agent; Epoxy compounds; Oxetane compounds; A light diffusing agent; A photopolymerization initiator; And an ultraviolet curable ink composition for forming a black bezel pattern comprising an organic solvent.
  • the present invention provides a method of manufacturing a light emitting device, comprising the steps of: a) inkjet printing the ultraviolet curable ink composition on a substrate to form a bezel pattern; And b) irradiating the bezel pattern with ultraviolet light to cure the bezel pattern.
  • the present invention also provides a method of forming a bezel pattern using the ultraviolet curable ink composition.
  • the present invention also provides a bezel pattern produced using the ultraviolet curable ink composition.
  • the present invention also provides a display substrate including the bezel pattern.
  • the ultraviolet curable black ink composition according to the present invention is a black bezel ink developed for application to a cover window film of a foldable display and has excellent light shielding property at a thin thickness, , It does not cause surface wrinkles caused by the difference in curing rate between the bezel and the bezel, and is excellent in thermal stability and curing sensitivity only by UV curing without a pretreatment process.
  • the ultraviolet curable ink composition according to the present invention comprises a black pigment; Dispersant; Epoxy compounds; Oxetane compounds; A light diffusing agent; A photopolymerization initiator; And organic solvents.
  • the black pigment includes at least one black ink pigment selected from the group consisting of carbon black, graphite, metal oxides and organic black pigments.
  • Examples of carbon blacks are cysteine 5HIISAF-HS, cysto KH, cysteo 3HHAF-HS, cysteo NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, , SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTO SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E Diagram G Diagram R Diagram N760M Diagram LR, # 2700, # 25, # 45, # 45, # 45, # 45, # 45, # 45, # 45, # 25, # CF9, # 95, # 20, # 2300, # 2350, # 2300, # 2200, # 1000, # 980, # 900, 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B
  • organic black pigment examples include aniline black, lactam black, perylene black, and the like, but the present invention is not limited thereto.
  • the content of the black pigment is 15 to 25% by weight, preferably 15 to 20% by weight based on the total ink composition, and when the content is less than 15% by weight based on the total ink composition, OD is not shown, and when it is more than 25% by weight, an excess amount of colorant may not be dispersed in the ink and a precipitate may be formed.
  • the dispersant is used to make the black pigment particles of a uniform size and to shorten the production time of the ink.
  • the dispersing agent may be a polymeric, nonionic, anionic or cationic dispersing agent.
  • examples of the dispersing agent include acrylic type, polyalkylene glycol and its esters, polyoxyalkylene polyhydric alcohol, ester alkylene oxide adduct, alcohol Alkylene oxide adducts, sulfonic acid esters, sulfonate salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts and alkyl amines, which may be used alone or in combination of two or more thereof , Storage stability of ink, and the like are preferably used.
  • the pigment may not be uniformly dispersed If it exceeds 5% by weight, the pigment may aggregate or the curing sensitivity may be lowered.
  • the epoxy compound is a cationic polymerization type and specifically includes a bisphenol type epoxy compound, a novolak type epoxy compound, a glycidyl ester type epoxy compound, a glycidylamine type epoxy compound, a linear aliphatic epoxy compound, a biphenyl type epoxy compound, Type epoxy compounds.
  • the alicyclic epoxy compound may mean a compound containing at least one epoxidized aliphatic cyclic group.
  • the epoxidized aliphatic cyclic group means an epoxy group bonded to an alicyclic ring, and examples thereof include 3,4-epoxycyclopentyl group, 3,4-epoxy (3,4-epoxycyclohexyl) ethyl group, a 3- (3,4-epoxycyclohexyl) ethyl group, an isopropylcyclopentylmethyl group, (3,4-epoxycyclopentyl) propyl group or 3- (3,4-epoxycyclohexyl) propyl group.
  • the hydrogen atom constituting the alicyclic ring may optionally be substituted with a substituent such as an alkyl group.
  • a substituent such as an alkyl group.
  • the alicyclic epoxy compound for example, a compound specifically exemplified below can be used, but epoxy compounds which can be used are not limited to the following types.
  • the content of the epoxy compound is preferably 3 to 60% by weight, more preferably 5 to 30% by weight based on the total weight of the ultraviolet curable ink composition. If the content of the epoxy compound exceeds 60% by weight, the viscosity of the ink composition increases to deteriorate the performance of the inkjet process. If the content of the epoxy compound is less than 3% by weight, the curing sensitivity may be deteriorated.
  • the oxetane compound is a cationically polymerizable monomer having a quaternary cyclic ether group in the molecular structure, and may act to lower the viscosity of the cationically cured ink composition (for example, less than 50 cP at 25 ⁇ ).
  • oxetane compound examples include "ARON OXETANE OXT-101", “ARON OXETAN OXT-121", “ARON OXETAN OXT-211", “ARON OXETAN OXT -221 " or " Alon oxetane OXT-212 " These may be used alone or in combination of two or more.
  • the content of the oxetane compound is preferably 15 to 80% by weight, more preferably 20 to 60% by weight based on the total weight of the ultraviolet curable ink composition. If it is more than 80% by weight, the curing sensitivity is low, and if it is less than 15% by weight, the viscosity increases and coating properties are deteriorated.
  • the light diffusing agent may be TiO 2 or Al 2 O 3 or a combination thereof as a material having a high surface reflectivity.
  • An ink composition having a high light-shielding property (for example, OD 5) as in the present invention may be UV- It is used for suppressing surface wrinkles that occur in the case of the above.
  • the light diffusing agent may have an average particle diameter of 0.1 to 5.0 mu m.
  • the content of the light diffusing agent may be 5 to 10% by weight, and preferably 5 to 8% by weight based on the total weight of the ultraviolet curable ink composition.
  • the content of the light diffusing agent is less than 5% by weight, the light diffusing effect is lowered and surface wrinkles are generated during UV curing.
  • the content of the light diffusing agent is more than 10% by weight, the inorganic filler content is increased, Problems arise.
  • the photopolymerization initiator is a cationic polymerizable initiator.
  • the photopolymerization initiator includes at least one kind of compound which produces cationic species or Bronsted acid by irradiation with ultraviolet rays, for example, an iodonium salt and a sulfonium salt.
  • the iodonium salt or sulfonium salt causes a curing reaction in which monomers having an unsaturated double bond contained in the ink react with each other to form a polymer in an ultraviolet curing process.
  • the photopolymerization initiator may be an anion represented by SbF 6 -, AsF 6 -, BF 6 -, (C 6 F 5 ) 4 B-, PF 6 - or Rf n F 6 -n , Irgacure 250, Irgacure 270, Irgacure 290, CPI-100P, CPI-101A, CPI-210S, Omnicat 440, Omnicat 550, Omnicat 650, etc. are commercially available. They may be used alone or in combination of two or more.
  • the photopolymerization initiator may be a sulfonium salt, more preferably 10- [1,1'-biphenyl] -4- 9-oxo-9H-thioxanetetanium hexafluorophosphate (10- [1,1'-Biphenyl] -4-yl- 2- (1-methylethyl) -9- oxo-9H-thioxanthenium hexafluorophosphate (Omnicat 550).
  • the content of the photopolymerization initiator is 1 to 10% by weight, preferably 2 to 7% by weight, more preferably 3 to 5% by weight based on the total ink composition.
  • the reaction may be insufficient, and if it exceeds 10% by weight, it may not be dissolved completely or the viscosity may be increased and the inkjet processability may be deteriorated.
  • the organic solvent may be used without particular limitation as long as it has excellent curing sensitivity even after printing the bezel pattern on the display substrate using the ink composition according to the present invention.
  • the black pigment when the black pigment is contained at a low content of less than 10% by weight (particularly 7% by weight or less) with respect to the total ink composition, an organic solvent such as ethylene glycol monobutyl ether acetate (BCSA) There is no serious problem in the performance of the inkjet process. However, when the black pigment is contained in the ink composition in an amount of 10% by weight or more, the inkjet process performance is degraded.
  • BCSA ethylene glycol monobutyl ether acetate
  • an organic solvent capable of improving or improving the performance of an inkjet process by allowing the ink composition to form a thin-walled bezel pattern while exhibiting high light shielding performance.
  • the organic solvent satisfying the conditions of high boiling point and low viscosity (boiling point of 200 ° C or higher and viscosity at 25 ° C of 1 cP to 5 cP, especially 3 cP or lower) as in the case of using an organic solvent satisfying these conditions is improved, For example, butyl diglyme or diethylene glycol dibutyl ether, dipropylene glycol methyl ether acetate, ethylene glycol dibutyrate, diethyl succinic acid, Diethyl succinate, gamma-butyrolactone (GBL), and ethyl caprate. And it is most preferred to use the butyl diglyme and diethyl succinate.
  • the content of the organic solvent is 10 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 35% by weight based on the total ink composition.
  • the content of the organic solvent is less than 10% by weight, Or the thickness of the bezel layer may become thick.
  • it exceeds 40% by weight the curing sensitivity may be lowered.
  • the ink composition according to the present invention may further include at least one of a reactive diluent, an adhesion promoting agent, and a surfactant, if necessary.
  • the reactive diluent may be included to improve the ink jet processability by lowering the viscosity of the ink.
  • a glycidyl ether-based epoxy compound capable of cationic polymerization may be used.
  • the glycidyl ether-based epoxy compound include N-butyl N-butyl glycidyl ether, and neopentyl glycol diglycidyl ether (LD203). One or more of them may be used.
  • the content of the reactive diluent is preferably 0 to 30% by weight, more preferably 0.1 to 20% by weight based on the total weight of the ultraviolet curable ink composition. If it is more than 30% by weight, the curing sensitivity is lowered.
  • the adhesion-promoting agent may improve adhesion of the substrate and the print layer, and may include at least one selected from the group consisting of an alkoxysilane compound and a phosphate-based acrylate such as phosphate acrylate,
  • the silane compound include 3-glycidoxypropyl trimethoxysilane, KBM-403 (Shin-Etsu Co., USA), 3-glycidoxypropyl methyldimethoxysilane KBM-402), 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, KBM-303, 3-glycidoxypropylmethyldiethoxysilane (3- Glycidoxypropyl methyldiethoxysilane, KBE-402), 3-glycidoxypropyl triethoxysilane (KBE-403), and 3-methacryloxypropyl trimethoxysilane ane, KBM-503), and one or more of them can be used.
  • the content thereof is 1 to 5% by weight, preferably 2 to 4% by weight based on the total ink composition.
  • the content of the adhesion promoting agent is less than 1% by weight, And if it is more than 5% by weight, the stability and curing sensitivity of the ink may be deteriorated.
  • the surface active agent controls the surface tension of the ink to smoothly jetting the ink, and also allows the ink to properly spread on the substrate.
  • the surfactant is commercially available from Dai Nippon Ink & Chemicals, Megafack F-444, F-475 , F-478, F-479, F-484, F-550, F-552, F-553, F-555, F-570 and RS-75, or Surflon S- , Fluorad FC-93, FC-95, FC-98, FC-129 and FC-135 of Sumitomo 3M, S-113, S-121, S-131, S- 310, BYK-320, BYK-320, BYK-330, BYK-300, FSN, FSN-100 and FSO from DuPont, 361, BYK-381, BYK-370, BYK-371, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-3
  • the content thereof is 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total ink composition.
  • the content of the surfactant is less than 0.1% by weight, The effect of lowering the tensile force is insufficient and coating failure phenomenon occurs when the composition is coated on the substrate.
  • the amount of the surfactant is more than 5% by weight, the surfactant is used in an excess amount and the compatibility and defoaming property of the composition is rather reduced Problems may arise.
  • the ultraviolet curable ink composition used in the present invention spreads within a short time immediately after inkjet printing, exhibits excellent coating film characteristics, and exhibits excellent adhesion properties by curing. Accordingly, when the ultraviolet curable ink composition is applied, it is preferable to provide a UV lamp immediately after the inkjet head so that curing can be performed simultaneously with inkjet printing.
  • the ultraviolet curable ink composition has a curing dose of 1 to 10,000 mJ / cm2, preferably 1,000 to 2,000 mJ / cm2.
  • the ultraviolet curable ink composition is cured by absorbing radiation in a wavelength range of 250 to 450 nm, preferably 360 to 410 nm.
  • the ultraviolet curable ink composition is suitable for an inkjet process, for example, by having a viscosity of 1 cP to 50 cP at 25 ⁇ , more preferably 3 cP to 45 cP at 25 ⁇ .
  • the ultraviolet curable ink composition having the viscosity range described above has good ejection at the process temperature.
  • the process temperature means a temperature at which the viscosity of the curable ink composition is lowered.
  • the process temperature may be from 10 ⁇ to 100 ⁇ , and preferably from 20 ⁇ to 70 ⁇ .
  • the ultraviolet curable ink composition has excellent adhesion to a substrate and coating property.
  • the bezel pattern formed according to the present invention with the ultraviolet ray curable ink composition is excellent in adhesion to a substrate, and the adhesive force with a substrate in a state where a post-process (heat treatment) is excluded is cross-cut test 4B or more.
  • a method of forming a bezel pattern using the ultraviolet curable ink composition comprises the steps of: a) inkjet printing a UV curable ink composition for inkjet according to claim 1 on a substrate to form a bezel pattern; And b) curing the bezel pattern by irradiating ultraviolet light.
  • the thickness of the cured bezel pattern may be 2 to 6 ⁇ ⁇ , or 2 to 4 ⁇ ⁇ , and a detailed description thereof will be given in connection with the description of the ink composition item, the bezel using a conventional cationic polymerization ink composition It follows the pattern formation method.
  • the present invention provides a bezel pattern prepared using the ultraviolet curable ink composition or manufactured according to the method of forming the bezel pattern.
  • the present invention also provides a display substrate including the bezel pattern.
  • the display may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display A liquid crystal display (LCD), a liquid crystal display (LCD), and a cathode ray tube (CRT).
  • PDP plasma display panel
  • LED light emitting diode
  • OLED organic light emitting diode
  • LCD liquid crystal display
  • LCD liquid crystal display
  • LCD liquid crystal display
  • CRT cathode ray tube
  • the black bezel pattern according to the present invention is formed on the transparent PI film or the hard coating layer included in the cover window of the foldable display, and has excellent light shielding property at a thin thickness, so that the visibility of the panel and the problem of step difference are not generated.
  • the surface wrinkles caused by the high shading property (OD 5) were suppressed by applying a light diffusing agent having a high ultraviolet reflectance when the UV curing was performed by printing at 1 degree, and the long-wavelength sulfonium cation photoinitiator was applied to improve heat stability and curing sensitivity Do.
  • the composition of the present invention can be printed at 2 degrees, if a bezel pattern is formed on the cover window film by printing at 1 degree, there is no alignment required for printing at 2 degrees, which can improve the process time and cost (yield) .
  • the UV curable ink composition of the present invention was prepared by stirring for 7 hours with a mixture of 7 wt% of CeLoxide 2021P, 25 wt% of oxetane OXT-221, 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) .
  • a pigment dispersion (18 wt% of carbon black, 5 wt% of TiO 2 , 4 wt% of dispersant, 30 wt% of diethyl succinate), 7 wt% of Celloxide 2021P, 25 wt% of cetane OXT-221, 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ultraviolet curable ink composition of the present invention.
  • KBM-403 3-glycidoxypropyltrimethoxysilane
  • Pigment dispersion (18 wt% carbon black, 5 wt% TiO2, 4 wt% dispersant, 30 wt% BCA), 7 wt% of Celloxide 20P, 25 wt% of oxetane OXT-221, 2 wt% of KBM- Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ink composition.
  • Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (CPI-210S) and 1% by weight of a sensitizer (DBA) were stirred and mixed for 5 hours to prepare an ink composition.
  • CPI-210S photoinitiator
  • DBA sensitizer
  • Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 25% by weight of oxetane OXT- , 4% by weight of a photoinitiator (UV692S), 4% by weight of GBL and 1% by weight of a sensitizer (DBA) for 5 hours to prepare an ink composition.
  • UV692S photoinitiator
  • GBL 4% by weight of GBL
  • DBA sensitizer
  • Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (Irgacure 290) and 1% by weight of a sensitizer (DBA) were stirred and mixed for 5 hours to prepare an ink composition.
  • a photoinitiator Irgacure 290
  • DBA sensitizer
  • Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (Irgacure 250) and 1% by weight of a sensitizer (ITX) were stirred and mixed for 5 hours to prepare an ink composition.
  • a photoinitiator Irgacure 250
  • ITX sensitizer
  • KBM-403 3-glycidoxypropyltrimethoxysilane
  • CPI-210S 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluoroethyl) trifluorophosphate
  • Irgacure 290 tetralis (2,3,4,5,6-pentafluorophenyl) boranoid; Tris [4- (4-acetylphenyl) sulfanylphenyl] sulfonium (Tris [4- (4-acetylphenyl) sulfanylphenyl]
  • Irgacure 250 75% solution of iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl], hexafluorophosphate (1-) in propylene carbonate (75% solution of Iodonium, -methylphenyl) [4- (2-methylpropyl) phenyl] -, hexafluorophosphate (1) in propylene carbonate)
  • the curing sensitivity was evaluated by measuring the UV energy at a tack free point at which the adhesive strength was lost using a UV LED lamp having a wavelength of 395 nm, and the adhesion was evaluated as 0B to 5B by a cross cut test (standard: ASTM D3002, D3359), inkjet processability was confirmed by jetting evaluation according to idle time after short purse (3s) and wiping with all nozzles out, Whether the wrinkles were wrinkled or not was visually confirmed.
  • the storage stability of the ink was confirmed by storing the ink in an oven at 45 ° C for less than 10% after one week.
  • compositions of Examples 1 to 4 according to the present invention are excellent in curing sensitivity, adhesive force, inkjet processability and storage stability, On the contrary, the composition of Comparative Example 1 had a lowered carbon black content to 12% in Example 2, and the reliability of the bezel increased to 5 ⁇ .
  • Example 2 surface wrinkles occurred in the ink in which the light diffusing agent was changed to 5% SiO 2.
  • Comparative Example 3 surface wrinkles occurred in the ink from which the light diffusing agent was removed in Example 2, and the composition of Comparative Example 4 Surface wrinkles occurred in the ink of Example 2 in which the content of the light diffusing agent TiO 2 was reduced to 3%.
  • Comparative Example 5 was degraded to less than one minute in inkjet processability with the ink of Example 1 changed to BCSA, and the composition of Comparative Example 6 was cured with the ink of Example 1 in which the solvent was changed to BCA 20,000 mJ / cm 2) was not good.
  • the composition of Comparative Example 7 had poor curing sensitivity (10,000 mJ / cm 2) in the ink in which the photopolymerization initiator was changed to CPI-210S in Example 2, and the composition of Comparative Example 8 had the UV- (12,000 mJ / cm < 2 >) was poor in the ink changed to 692S, and the composition of Comparative Example 9 had poor curing sensitivity (15,000 mJ / cm < 2 >) in the ink of Example 2 in which the photopolymerization initiator was changed to Irgacure 290,
  • the composition of Comparative Example 10 was good in curing sensitivity (6,000 mJ / cm 2) with an ink prepared by changing the photopolymerization initiator to Irgacure 250 in Example 2, but the storage stability (45 ° C for one week storage, viscosity increase of 10% or more) was not good.

Abstract

The present invention relates to an ultraviolet curable black ink composition, a bezel pattern forming method using the same, a bezel pattern produced by the method, and a display substrate comprising the bezel pattern, wherein the ultraviolet curable black ink composition is black bezel ink developed to be applied to a cover window film of a foldable display, has excellent light shielding properties and folding properties at a thin thickness, and as a light diffusing agent is applied to the ink, prevents surface wrinkles from generating due to a difference in the curing rate of the upper and lower portions of a bezel, by means of UV curing alone without a pretreatment process.

Description

폴더블 디스플레이의 자외선 경화형 블랙 잉크 조성물 및 이를 이용한 베젤패턴의 형성방법UV-curable black ink composition of a foldable display and method of forming a bezel pattern using the composition
본 출원은 2017년 12월 14일자로 출원된 대한민국 특허출원 제10-2017-0171970호 및 2018년 12월 10일자로 출원된 대한민국 특허출원 제10-2018-0157794호에 기초한 우선권의 이익을 주장하며, 해당 대한민국 특허출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0171970 filed on December 14, 2017, and Korean Patent Application No. 10-2018-0157794 filed on December 10, 2018 , The contents of which are incorporated herein by reference in their respective Korean patent applications.
본 발명은 폴더블 디스플레이의 자외선 경화형 블랙 잉크 조성물, 이를 이용한 베젤패턴의 형성방법, 이에 따라 제조한 베젤패턴 및 이를 포함하는 디스플레이 기판에 관한 것이다.The present invention relates to a UV curable black ink composition for a foldable display, a method of forming a bezel pattern using the same, a bezel pattern manufactured thereby, and a display substrate comprising the same.
플렉시블 디스플레이 시장은 평면과 커브드 제품에서 자유롭게 접었다 펼 수 있는 폴더블 제품으로 진화하고 있으며, 폴더블 디스플레이도 다른 디스플레이 기기와 마찬가지로 패널의 비표시 영역 패턴이 시인되지 않으면서, 색감을 주기 위한 베젤패턴이 필요하다. 모바일 기기 특성상 사람의 눈과 가까운 거리에 접하기 때문에 패널 패턴이 시인되지 않으려면 차광 특성이 높은 베젤을 형성해야 하지만, 베젤이 두꺼워지면 베젤 단차가 화면부에서 시인되는 문제가 발생한다. 이를 해결하기 위해서는 두께는 얇으면서 차광특성은 우수한 베젤패턴이 필요하며, 고 차광 블랙잉크를 1도 인쇄(single layer printing)로 한번에 UV 경화하기 위해서 표면주름을 억제할 수 있는 잉크 조성이 요구된다.The flexible display market has evolved into a foldable product that can be freely folded and unfolded in both flat and curved products. Foldable display, like other display devices, has a bezel pattern Is required. In order to prevent the panel pattern from being visually recognized due to the nature of the mobile device, the bezel should have a high light shielding property. However, when the bezel becomes thick, the bezel step is visually recognized on the screen. In order to solve this problem, a bezel pattern having a thin thickness and excellent light shielding property is required, and an ink composition capable of suppressing surface wrinkling is required in order to UV cure the high light-shielding black ink by single layer printing.
대한민국 특허공개 제10-2016-0147535호에서는 잉크젯 공정으로 베젤을 형성할 수 있는 자외선 경화 블랙 잉크를 개발하였지만 TV 제품에 적용하는 잉크로 차광특성(광학밀도(optical density, O.D) 1@2.2㎛)이 낮아 패널 패턴 시인문제로 폴더블에 적용하기 어렵다. 대한민국 특허공개 제10-2016-0046723호는 1도 인쇄로 차광특성이 높은 잉크를 개발하였지만 표면주름을 억제하기 위해 UV 경화 전에 열처리 공정을 적용하였다. 또한, 상기 선행문헌들에 개시된 잉크는 유리기판에 적용하기 위해 개발된 베젤잉크로 폴더블 커버윈도우 필름에 적용하기 어렵다.Korean Patent Laid-Open Publication No. 10-2016-0147535 has developed an ultraviolet curable black ink capable of forming a bezel by an inkjet process. However, it has a light shielding property (optical density (OD) 1@2.2 μm) It is difficult to apply it to the folder blind due to the problem of visibility of the panel pattern. Korean Patent Laid-Open Publication No. 10-2016-0046723 has developed an ink having a high light-shielding property by printing at 1 degree, but a heat treatment process is applied before UV curing to suppress surface wrinkles. In addition, the inks disclosed in the above prior art documents are difficult to apply to a foldable cover window film with bezel ink developed for application to glass substrates.
이에, 얇은 두께에서 차광특성 및 폴딩 특성이 우수하며, UV 경화만으로도 베젤 상, 하부의 경화율 차이에 의해 생기는 표면주름이 발생하지 않는, 폴더블 디스플레이의 커버 윈도우 필름에 적용하기 위한 블랙 베젤잉크의 개발이 요구된다.Thus, a black bezel ink for application to a cover window film of a foldable display, which has excellent light shielding property and folding property at a thin thickness, and which does not cause surface wrinkling caused by difference in curing rate between the bezel upper and lower bezel only by UV curing Development is required.
본 발명의 목적은, 폴더블 디스플레이의 커버 윈도우 필름에 적용하기 위해 개발된 블랙 베젤잉크로 얇은 두께에서 차광특성 및 폴딩 특성이 우수하며, 잉크에 광 확산제를 적용하여 전처리 공정없이 UV 경화만으로도 베젤 상, 하부의 경화율 차이에 의해 생기는 표면주름이 발생하지 않는 자외선 경화형 블랙 잉크 조성물 및 이를 이용한 베젤패턴의 형성방법, 이에 따라 제조한 베젤패턴, 및 이를 포함하는 디스플레이 기판을 제공하는 것이다.It is an object of the present invention to provide a black bezel ink which is developed for application to a cover window film of a foldable display and has excellent light shielding property and folding property at a thin thickness and a light diffusing agent is applied to the ink, The present invention provides a method of forming an ultraviolet curable black ink composition which does not cause surface wrinkles caused by a difference in curing rate between the upper and lower portions, a method of forming a bezel pattern using the same, a bezel pattern manufactured thereby, and a display substrate comprising the same.
상기 목적을 달성하기 위하여, 본 발명은 블랙 안료; 분산제; 에폭시 화합물; 옥세탄 화합물; 광확산제; 광중합 개시제; 및 유기 용매를 포함하는 블랙 베젤패턴 형성용 자외선 경화형 잉크 조성물을 제공한다. In order to achieve the above object, the present invention provides a black pigment, Dispersing agent; Epoxy compounds; Oxetane compounds; A light diffusing agent; A photopolymerization initiator; And an ultraviolet curable ink composition for forming a black bezel pattern comprising an organic solvent.
또한, 본 발명은 a) 기판에 상기 자외선 경화형 잉크 조성물을 잉크젯 프린팅하여, 베젤패턴을 형성하는 단계; 및 b) 상기 베젤패턴에 자외선을 조사하여 경화하는 단계를 포함하는 자외선 경화형 잉크 조성물을 이용한 베젤패턴의 형성방법을 제공한다.Also, the present invention provides a method of manufacturing a light emitting device, comprising the steps of: a) inkjet printing the ultraviolet curable ink composition on a substrate to form a bezel pattern; And b) irradiating the bezel pattern with ultraviolet light to cure the bezel pattern. The present invention also provides a method of forming a bezel pattern using the ultraviolet curable ink composition.
또한, 본 발명은 상기 자외선 경화형 잉크 조성물을 사용하여 제조한 베젤패턴을 제공한다.The present invention also provides a bezel pattern produced using the ultraviolet curable ink composition.
또한, 본 발명은 상기 베젤패턴을 포함하는 디스플레이 기판을 제공한다.The present invention also provides a display substrate including the bezel pattern.
본 발명에 따른 자외선 경화형 블랙 잉크 조성물은 폴더블 디스플레이의 커버 윈도우 필름에 적용하기 위해 개발된 블랙 베젤잉크로, 얇은 두께에서 차광 특성이 우수하여 패널의 패턴 시인성 및 단차 시인 문제가 발생하지 않고, 잉크에 광확산제를 적용하여 전처리 공정없이 UV 경화만으로도 베젤 상, 하부의 경화율 차이에 의해 생기는 표면주름이 발생하지 않으며, 열 안정성 및 경화감도가 우수하다.The ultraviolet curable black ink composition according to the present invention is a black bezel ink developed for application to a cover window film of a foldable display and has excellent light shielding property at a thin thickness, , It does not cause surface wrinkles caused by the difference in curing rate between the bezel and the bezel, and is excellent in thermal stability and curing sensitivity only by UV curing without a pretreatment process.
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시양태를 가질 수 있는 바, 특정 실시양태들을 예시하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태로 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.The present invention is capable of various modifications and various embodiments and is intended to illustrate certain embodiments. It should be understood, however, that the present invention is not intended to be limited to any particular embodiment, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
본 발명에 따른 자외선 경화형 잉크 조성물은 블랙 안료; 분산재; 에폭시 화합물; 옥세탄 화합물; 광확산제; 광중합 개시제; 및 유기 용매를 포함한다.The ultraviolet curable ink composition according to the present invention comprises a black pigment; Dispersant; Epoxy compounds; Oxetane compounds; A light diffusing agent; A photopolymerization initiator; And organic solvents.
상기 블랙 안료는 카본 블랙, 흑연, 금속 산화물 및 유기블랙 안료로 이루어지는 군에서 선택되는 1종 이상의 블랙 잉크 안료를 포함한다.The black pigment includes at least one black ink pigment selected from the group consisting of carbon black, graphite, metal oxides and organic black pigments.
카본 블랙의 예로는 시스토 5HIISAF-HS, 시스토 KH, 시스토 3HHAF-HS, 시스토 NH, 시스토 3M, 시스토 300HAF-LS, 시스토 116HMMAF-HS, 시스토 116MAF, 시스토 FMFEF-HS, 시스토 SOFEF, 시스토VGPF, 시스토 SVHSRF-HS 및 시스토 SSRF(동해카본 ㈜); 다이어그램 블랙 II, 다이어그램 블랙 N339, 다이어그램 블랙 SH, 다이어그램 블랙 H, 다이어그램 LH, 다이어그램 HA, 다이어그램 SF, 다이어그램 N550M, 다이어그램 M, 다이어그램 E, 다이어그램 G, 다이어그램 R, 다이어그램 N760M, 다이어그램 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 및 OIL31B(미쯔비시화학㈜); 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, 및 LAMP BLACK-101(데구사㈜); 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, 및 RAVEN-1170(콜롬비아 카본㈜) 또는 이들의 혼합물 등을 들 수 있다.Examples of carbon blacks are cysteine 5HIISAF-HS, cysto KH, cysteo 3HHAF-HS, cysteo NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, , SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTO SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E Diagram G Diagram R Diagram N760M Diagram LR, # 2700, # 25, # 45, # 45, # 45, # 45, # 45, # 25, # CF9, # 95, # 20, # 2300, # 2350, # 2300, # 2200, # 1000, # 980, # 900, 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical); PRINTEX-25, PRINTEX-25, PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX- SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (manufactured by Degussa); PRINTEX-40, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; SPECIAL BLACK-350; 890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850R, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1040ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN- RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 (Colombia Carbon) or mixtures thereof.
상기 유기블랙 안료로 아닐린 블랙, 락탐 블랙 또는 페릴렌 블랙계열 등을 사용할 수 있으나, 이로 한정하는 것은 아니다.Examples of the organic black pigment include aniline black, lactam black, perylene black, and the like, but the present invention is not limited thereto.
상기 블랙 안료의 함량은 전체 잉크 조성물에 대하여, 15 내지 25중량%, 바람직하게는 15 내지 20중량%로서, 상기 함량이 전체 잉크 조성물에 대하여 15중량% 미만일 경우에는, 베젤에 적용할 만한 수준의 O.D가 나타나지 않으며, 25중량% 초과일 경우, 과량의 착색제가 잉크에 분산되지 않고 침전물이 형성될 수 있다.The content of the black pigment is 15 to 25% by weight, preferably 15 to 20% by weight based on the total ink composition, and when the content is less than 15% by weight based on the total ink composition, OD is not shown, and when it is more than 25% by weight, an excess amount of colorant may not be dispersed in the ink and a precipitate may be formed.
상기 분산제는 상기 블랙 안료를 균일한 크기의 입자로 만들고, 또한, 잉크의 제조 시간을 단축시키기 위하여 사용된다. 상기 분산제로는 고분자형, 비이온성, 음이온성 또는 양이온성의 분산제를 사용할 수 있으며, 그 예로는 아크릴 계열, 폴리알킬렌글리콜 및 이의 에스테르, 폴리옥시알킬렌 다가 알코올, 에스테르알킬렌 옥사이드 부가물, 알코올알킬렌옥사이드 부가물, 설폰산 에스테르, 설폰산염, 카르복실산에스테르, 카르복실산염, 알킬아미드알킬렌옥사이드 부가물 및 알킬아민 등이 있고, 단독으로 사용하거나 둘 이상 혼합하여 사용할 수 있으며, 이 중, 잉크의 저장성 등이 우수한 아크릴 계열의 분산제를 사용하는 것이 바람직하다.The dispersant is used to make the black pigment particles of a uniform size and to shorten the production time of the ink. The dispersing agent may be a polymeric, nonionic, anionic or cationic dispersing agent. Examples of the dispersing agent include acrylic type, polyalkylene glycol and its esters, polyoxyalkylene polyhydric alcohol, ester alkylene oxide adduct, alcohol Alkylene oxide adducts, sulfonic acid esters, sulfonate salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts and alkyl amines, which may be used alone or in combination of two or more thereof , Storage stability of ink, and the like are preferably used.
상기 분산제의 함량은 전체 잉크 조성물에 대하여 0.5 내지 5중량%, 또는 2 내지 4중량%로서, 상기 분산제의 함량이 전체 잉크 조성물에 대하여 0.5중량% 미만일 경우에는, 안료가 고르게 분산되지 않을 우려가 있고, 5중량%를 초과할 경우에는, 안료가 응집되거나 경화감도가 저하될 우려가 있다.If the content of the dispersing agent is less than 0.5% by weight based on the total ink composition, the pigment may not be uniformly dispersed If it exceeds 5% by weight, the pigment may aggregate or the curing sensitivity may be lowered.
상기 에폭시 화합물은 양이온 중합형으로서, 구체적으로 비스페놀형 에폭시 화합물, 노볼락형 에폭시 화합물, 글리시딜 에스테르형 에폭시 화합물, 글리시딜 아민형 에폭시 화합물, 선형 지방족 에폭시 화합물, 비페닐형 에폭시 화합물 및 지환식 에폭시 화합물 중에서 선택되는 1종 이상일 수 있다.The epoxy compound is a cationic polymerization type and specifically includes a bisphenol type epoxy compound, a novolak type epoxy compound, a glycidyl ester type epoxy compound, a glycidylamine type epoxy compound, a linear aliphatic epoxy compound, a biphenyl type epoxy compound, Type epoxy compounds.
상기 지환식 에폭시 화합물은, 에폭시화 지방족 고리기를 하나 이상 포함하는 화합물을 의미할 수 있다.The alicyclic epoxy compound may mean a compound containing at least one epoxidized aliphatic cyclic group.
에폭시화 지방족 고리기를 포함하는 상기 지환족 에폭시 화합물에서, 상기 에폭시화 지방족 고리기는 지환식 고리에 결합된 에폭시기를 의미하는 것으로, 예를 들면, 3,4-에폭시시클로펜틸기, 3,4-에폭시시클로헥실기, 3,4-에폭시시클로펜틸메틸기, 3,4-에폭시시클로헥실메틸기, 2-(3,4-에폭시시클로펜틸)에틸기, 2-(3,4-에폭시시클로헥실)에틸기, 3-(3,4-에폭시시클로페틸)프로필기 또는 3-(3,4-에폭시시클로헥실)프로필기 등의 관능기가 예시될 수 있다. 상기에서 지환식 고리를 구성하는 수소 원자는, 임의적으로 알킬기 등의 치환기에 의해 치환될 수도 있다. 상기 지환식 에폭시 화합물로는, 예를 들면, 이하에서 구체적으로 예시되는 화합물을 사용할 수 있으나, 사용할 수 있는 에폭시 화합물이 하기의 종류에 제한되는 것은 아니다.In the above-mentioned cycloaliphatic epoxy compound containing an epoxidized aliphatic cyclic group, the epoxidized aliphatic cyclic group means an epoxy group bonded to an alicyclic ring, and examples thereof include 3,4-epoxycyclopentyl group, 3,4-epoxy (3,4-epoxycyclohexyl) ethyl group, a 3- (3,4-epoxycyclohexyl) ethyl group, an isopropylcyclopentylmethyl group, (3,4-epoxycyclopentyl) propyl group or 3- (3,4-epoxycyclohexyl) propyl group. The hydrogen atom constituting the alicyclic ring may optionally be substituted with a substituent such as an alkyl group. As the alicyclic epoxy compound, for example, a compound specifically exemplified below can be used, but epoxy compounds which can be used are not limited to the following types.
예컨대 디시클로펜타디엔디옥사이드, 시클로헥센옥사이드, 4-비닐-1,2-에폭시-4-비닐시클로헥센, 비닐시클로헥센디옥사이드, 리모넨모노옥사이드, 리모넨디옥사이드, (3,4-에폭시시클로헥실)메틸-3,4-에폭시시클로헥산카르복실레이트, 3-비닐시클로헥센옥사이드, 비스(2,3-에폭시시클로펜틸)에테르, 비스(3,4-에폭시시클로헥실메틸)아디페이트, 비스(3,4-에폭시-6-메틸시클로헥실메틸)아디페이트, (3,4-에폭시시클로헥실)메틸알코올, (3,4-에폭시-6-메틸시클로헥실)메틸-3,4-에폭시-6-메틸시클로헥산카르복실레이트, 에틸렌글리콜비스(3,4-에폭시시클로헥실)에테르, 3,4-에폭시시클로헥센카르본산 에틸렌글리콜디에스테르, (3,4-에폭시시클로헥실)에틸트리메톡시실란, 다이셀 코포레이션사의 셀록사이드(Celloxide) 8000, 셀록사이드 2021P 등을 사용할 수 있다.Vinylcyclohexene, vinylcyclohexene dioxide, limonene monoxide, limonene dioxide, (3,4-epoxycyclohexyl) methyl-cyclohexanecarboxylic acid, dicyclopentadiene oxide, cyclohexene oxide, (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylate, 3-vinylcyclohexene oxide, bis Epoxycyclohexylmethyl) adipate, (3,4-epoxycyclohexyl) methyl alcohol, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexane (3,4-epoxycyclohexyl) ether, 3,4-epoxycyclohexene carboxylic acid ethylene glycol diester, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Celloxide 8000, Celloxide 2021P and the like can be used.
상기 에폭시 화합물의 함량은 상기 자외선 경화형 잉크 조성물의 총 중량에 대하여 3 내지 60중량%인 것이 바람직하며, 보다 바람직하게는 5 내지 30중량%일 수 있다. 상기 에폭시 화합물의 함량이 60중량%를 초과하면 잉크 조성물의 점도가 상승하여 잉크젯 공정성능이 저하되고, 3중량% 미만이면 경화 감도가 저하될 수 있다.The content of the epoxy compound is preferably 3 to 60% by weight, more preferably 5 to 30% by weight based on the total weight of the ultraviolet curable ink composition. If the content of the epoxy compound exceeds 60% by weight, the viscosity of the ink composition increases to deteriorate the performance of the inkjet process. If the content of the epoxy compound is less than 3% by weight, the curing sensitivity may be deteriorated.
상기 옥세탄 화합물은 양이온 중합성 단량체로서 분자 구조 내에 4원 고리형 에테르기를 가지는 화합물이고, 양이온성 경화된 잉크 조성물의 점도를 낮추는(일례로, 25℃에서 50cP 미만) 작용을 할 수 있다. The oxetane compound is a cationically polymerizable monomer having a quaternary cyclic ether group in the molecular structure, and may act to lower the viscosity of the cationically cured ink composition (for example, less than 50 cP at 25 캜).
구체적으로는, 3-에틸-3-히드록시메틸 옥세탄, 1,4-비스[(3-에틸-3-옥세타닐)메톡시메틸]벤젠, 3-에틸-3-(페녹시메틸)옥세탄, 디[(3-에틸-3-옥세타닐)메틸]에테르, 3-에틸-3-(2-에틸헥실옥시메틸)옥세탄, 3-에틸-3-시클로헥실옥시메틸 옥세탄 또는 페놀노볼락 옥세탄 등이 예시될 수 있다. 옥세탄 화합물로는, 예를 들면, 토아고세이㈜의 「알론옥세탄(ARON OXETANE) OXT-101」, 「알론옥세탄 OXT-121」, 「알론옥세탄 OXT-211」, 「알론옥세탄 OXT-221」 또는 「알론옥세탄 OXT-212」 등을 사용할 수 있다. 이들은 단독으로, 혹은 2종 이상을 조합하여 이용할 수 있다.Specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-cyclohexyloxymethyloxetane or Phenol novolak oxetane, and the like. Examples of the oxetane compound include "ARON OXETANE OXT-101", "ARON OXETAN OXT-121", "ARON OXETAN OXT-211", "ARON OXETAN OXT -221 " or " Alon oxetane OXT-212 " These may be used alone or in combination of two or more.
상기 옥세탄 화합물의 함량은 상기 자외선 경화형 잉크 조성물의 총 중량에 대하여 15 내지 80중량%인 것이 바람직하며, 보다 바람직하게는 20 내지 60중량%일 수 있다. 80중량%를 초과하면 경화 감도가 낮고, 15중량% 미만이면 점도가 상승하여 코팅성이 저하된다. The content of the oxetane compound is preferably 15 to 80% by weight, more preferably 20 to 60% by weight based on the total weight of the ultraviolet curable ink composition. If it is more than 80% by weight, the curing sensitivity is low, and if it is less than 15% by weight, the viscosity increases and coating properties are deteriorated.
상기 광확산제는 표면반사율이 높은 재료로 TiO 2 또는 Al 2O 3 또는 이의 조합을 사용할 수 있으며, 본 발명과 같이 높은 차광특성(예컨대, O.D 5)을 갖는 잉크 조성물을 1도 인쇄로 UV 경화할 경우 발생하는 표면주름을 억제하기 위하여 사용된다.The light diffusing agent may be TiO 2 or Al 2 O 3 or a combination thereof as a material having a high surface reflectivity. An ink composition having a high light-shielding property (for example, OD 5) as in the present invention may be UV- It is used for suppressing surface wrinkles that occur in the case of the above.
상기 광확산제는 평균입경이 0.1 내지 5.0㎛일 수 있다.The light diffusing agent may have an average particle diameter of 0.1 to 5.0 mu m.
상기 광확산제의 함량은 상기 자외선 경화형 잉크 조성물의 총 중량에 대하여 5 내지 10중량%일 수 있고, 바람직하게는 5 내지 8중량%일 수 있다. 상기 광확산제의 함량이 5중량% 미만인 경우 광 확산 효과가 저하되어 UV 경화 시 표면주름이 발생하는 문제가 있고, 10중량%를 초과하는 경우 무기 충진재(filler) 함량이 높아져 잉크젯 공정성이 저하되는 문제가 초래된다.The content of the light diffusing agent may be 5 to 10% by weight, and preferably 5 to 8% by weight based on the total weight of the ultraviolet curable ink composition. When the content of the light diffusing agent is less than 5% by weight, the light diffusing effect is lowered and surface wrinkles are generated during UV curing. On the other hand, when the content of the light diffusing agent is more than 10% by weight, the inorganic filler content is increased, Problems arise.
상기 광중합 개시제는 양이온 중합성의 개시제로서, 구체적으로는 자외선 조사에 의해 양이온(cation) 종이나 브론스테드산을 만들어내는 화합물, 예를 들면 요오드늄 염 및 설포늄 염 중 적어도 1종을 포함한다. 상기 요오드늄 염 또는 설포늄 염은, 자외선 경화 과정에서 잉크에 함유된 불포화 이중결합을 가지는 모노머가 반응하여 고분자를 형성하는 경화 반응이 일어나도록 한다. 일 예로, 상기 광중합 개시제는 SbF 6-, AsF 6-, BF 6-, (C 6F 5) 4B-, PF 6- 또는 Rf nF 6-n으로 표시되는 음이온을 가지는 것일 수 있으나, 반드시 이에 한정되는 것은 아니며, 현재 시판되고 있는 상품으로는 Irgacure 250, Irgacure 270, Irgacure 290, CPI-100P, CPI-101A, CPI-210S, Omnicat 440 및 Omnicat 550, Omnicat 650 등이 있고, 이들 광중합 개시제는 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 특히, 본 발명의 일 양태에서, 자외선 경화형 잉크 조성물의 저장 안정성을 개선하기 위해, 상기 광중합 개시제는 설포늄 염일 수 있으며, 보다 바람직하게는 10-[1,1'-바이페닐]-4-일-2-(1-메틸에틸)-9-옥소-9H-티오크산테늄 헥사플루오로포스페이트(10-[1,1'-Biphenyl]-4-yl-2-(1-methylethyl)-9-oxo-9H-thioxanthenium hexafluorophosphate)(Omnicat 550)일 수 있다. The photopolymerization initiator is a cationic polymerizable initiator. Specifically, the photopolymerization initiator includes at least one kind of compound which produces cationic species or Bronsted acid by irradiation with ultraviolet rays, for example, an iodonium salt and a sulfonium salt. The iodonium salt or sulfonium salt causes a curing reaction in which monomers having an unsaturated double bond contained in the ink react with each other to form a polymer in an ultraviolet curing process. For example, the photopolymerization initiator may be an anion represented by SbF 6 -, AsF 6 -, BF 6 -, (C 6 F 5 ) 4 B-, PF 6 - or Rf n F 6 -n , Irgacure 250, Irgacure 270, Irgacure 290, CPI-100P, CPI-101A, CPI-210S, Omnicat 440, Omnicat 550, Omnicat 650, etc. are commercially available. They may be used alone or in combination of two or more. In particular, in one embodiment of the present invention, in order to improve the storage stability of the ultraviolet curable ink composition, the photopolymerization initiator may be a sulfonium salt, more preferably 10- [1,1'-biphenyl] -4- 9-oxo-9H-thioxanetetanium hexafluorophosphate (10- [1,1'-Biphenyl] -4-yl- 2- (1-methylethyl) -9- oxo-9H-thioxanthenium hexafluorophosphate (Omnicat 550).
상기 광중합 개시제의 함량은 전체 잉크 조성물에 대하여 1 내지 10중량%, 바람직하게는 2 내지 7중량%, 더욱 바람직하게는 3 내지 5중량%로서, 상기 광중합 개시제의 함량이 1중량% 미만일 경우에는 경화 반응이 충분하지 못할 우려가 있고, 10중량%를 초과할 경우에는 모두 용해되지 않거나, 점도가 증가하여 잉크젯 공정성이 저하될 수 있다.The content of the photopolymerization initiator is 1 to 10% by weight, preferably 2 to 7% by weight, more preferably 3 to 5% by weight based on the total ink composition. When the content of the photopolymerization initiator is less than 1% The reaction may be insufficient, and if it exceeds 10% by weight, it may not be dissolved completely or the viscosity may be increased and the inkjet processability may be deteriorated.
상기 유기 용매는, 본 발명에 따른 잉크 조성물을 이용하여 디스플레이 기판에 베젤패턴을 인쇄한 후에도, 경화감도가 우수한 것이라면 특별한 제한 없이 사용할 수 있으나, 잉크젯 공정 성능을 향상시키기 위하여, 비점이 200℃ 이상이고, 25℃에서 점도가 1cP 내지 5cP, 바람직하게는 3cP 이하인 것을 사용하는 것이 좋다.The organic solvent may be used without particular limitation as long as it has excellent curing sensitivity even after printing the bezel pattern on the display substrate using the ink composition according to the present invention. However, in order to improve the performance of the inkjet process, , And has a viscosity of 1 cP to 5 cP, preferably 3 cP or less at 25 캜.
즉, 상기 블랙 안료가 전체 잉크 조성물에 대해 10중량% 미만(특히, 7중량% 이하)의 낮은 함량으로 포함될 경우에는, 비점이 200℃ 미만인 에틸렌글리콜 모노부틸에테르 아세테이트(BCsA)와 같은 유기 용매를 사용하더라도 잉크젯 공정 성능에 큰 문제가 없지만, 잉크 조성물에 상기 블랙 안료가 10중량% 이상의 함량으로 포함될 경우에는, 잉크젯 공정 성능이 저하된다.That is, when the black pigment is contained at a low content of less than 10% by weight (particularly 7% by weight or less) with respect to the total ink composition, an organic solvent such as ethylene glycol monobutyl ether acetate (BCSA) There is no serious problem in the performance of the inkjet process. However, when the black pigment is contained in the ink composition in an amount of 10% by weight or more, the inkjet process performance is degraded.
따라서, 본 발명에서는, 상기 잉크 조성물이 높은 차광성을 나타내면서 얇은 두께의 베젤패턴을 형성할 수 있도록 하여 잉크젯 공정 성능을 향상 또는 개선시킬 수 있는 유기 용매의 사용이 요구되는데, 잉크젯 공정 성능은 상술한 바와 같은 고비점 및 저점도의 조건(비점이 200℃ 이상이고, 25℃에서 점도가 1cP 내지 5cP, 특히, 3cP 이하)을 만족하는 유기 용매를 사용할수록 향상되므로, 이와 같은 조건을 만족하는 유기 용매, 예를 들어, 부틸 다이글라임(Butyl diglyme, 또는 디에틸렌글리콜 디부틸에테르), 디프로필렌글리콜 메틸에테르 아세테이트(Dipropylene glycol methyl ether acetate), 에틸렌글리콜 디부티레이트(ethylene glycol dibutyrate), 디에틸 숙신산(Diethyl succinate), 감마부티로락톤(gamma-butyrolactone: GBL) 및 에틸 카프레이트(Ethyl caprate)와 같은 유기 용매를 사용하여야 하며, 상기 부틸 다이글라임 및 디에틸 숙신산을 사용하는 것이 가장 바람직하다.Therefore, in the present invention, it is required to use an organic solvent capable of improving or improving the performance of an inkjet process by allowing the ink composition to form a thin-walled bezel pattern while exhibiting high light shielding performance. As the organic solvent satisfying the conditions of high boiling point and low viscosity (boiling point of 200 ° C or higher and viscosity at 25 ° C of 1 cP to 5 cP, especially 3 cP or lower) as in the case of using an organic solvent satisfying these conditions is improved, For example, butyl diglyme or diethylene glycol dibutyl ether, dipropylene glycol methyl ether acetate, ethylene glycol dibutyrate, diethyl succinic acid, Diethyl succinate, gamma-butyrolactone (GBL), and ethyl caprate. And it is most preferred to use the butyl diglyme and diethyl succinate.
상기 유기 용매의 함량은 전체 잉크 조성물에 대하여 10 내지 40중량%, 바람직하게는 20 내지 35중량%, 더욱 바람직하게는 25 내지 35중량%로서, 상기 유기 용매의 함량이 10중량% 미만일 경우에는 잉크의 점도가 높아지거나 베젤층의 두께가 두꺼워질 우려가 있고, 40중량%를 초과할 경우에는 경화감도가 낮아지는 문제가 발생할 수 있다.The content of the organic solvent is 10 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 35% by weight based on the total ink composition. When the content of the organic solvent is less than 10% by weight, Or the thickness of the bezel layer may become thick. When it exceeds 40% by weight, the curing sensitivity may be lowered.
한편, 본 발명에 따른 잉크 조성물은, 필요에 따라, 반응성 희석제, 부착력 증진제 및 계면활성제 중 1종 이상을 더 포함할 수 있다. Meanwhile, the ink composition according to the present invention may further include at least one of a reactive diluent, an adhesion promoting agent, and a surfactant, if necessary.
상기 반응성 희석제는 잉크의 점도를 저하시켜 잉크젯 공정성을 개선하기 위해 포함될 수 있고, 양이온 중합이 가능한 글리시딜에테르계 에폭시 화합물을 사용할 수 있으며, 상기 글리시딜에테르계 에폭시 화합물의 예로는 N-부틸 글리시딜 에테르(N-Butyl Glycidyl Ether), 네오펜틸 글리콜 다이글리시딜 에테르(Neopentyl glycol diglycidyl ether, LD203) 등을 들 수 있고, 1종 이상 사용할 수 있다.The reactive diluent may be included to improve the ink jet processability by lowering the viscosity of the ink. A glycidyl ether-based epoxy compound capable of cationic polymerization may be used. Examples of the glycidyl ether-based epoxy compound include N-butyl N-butyl glycidyl ether, and neopentyl glycol diglycidyl ether (LD203). One or more of them may be used.
상기 반응성 희석제의 함량은 자외선 경화형 잉크 조성물의 총 중량에 대하여 0 내지 30중량%인 것이 바람직하며, 보다 바람직하게는 0.1 내지 20중량%일 수 있다. 30중량% 초과이면 경화 감도가 저하된다.The content of the reactive diluent is preferably 0 to 30% by weight, more preferably 0.1 to 20% by weight based on the total weight of the ultraviolet curable ink composition. If it is more than 30% by weight, the curing sensitivity is lowered.
상기 부착력 증진제는 기재와 인쇄층의 부착력을 향상시킬 수 있는 것으로서, 알콕시 실란 화합물 및 포스페이트 아크릴레이트(phosphate acrylate) 등의 포스페이트계 아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상의 것을 사용할 수 있으며, 상기 알콕시 실란 화합물의 예로는, 3-글리시독시프로필 트리메톡시실란(3-Glycidoxypropyl trimethoxysilane, KBM-403(Shin-Etsu사, 미국)), 3-글리시독시프로필 메틸디메톡시실란(3-Glycidoxypropyl methyldimethoxysilane, KBM-402), 2-(3,4 에폭시사이클로헥실)에틸트리메톡시실란(2-(3,4 epoxycyclohexyl) ethyltrimethoxysilane, KBM-303), 3-글리시독시프로필 메틸디에톡시실란(3-Glycidoxypropyl methyldiethoxysilane, KBE-402), 3-글리시독시프로필 트리에톡시실란(3-Glycidoxypropyl triethoxysilane, KBE-403) 및 3-메타크릴옥시프로필 트리메톡시실란(3-Methacryloxypropyl trimethoxysilane, KBM-503) 등을 들 수 있고, 1종 이상 사용할 수 있다.The adhesion-promoting agent may improve adhesion of the substrate and the print layer, and may include at least one selected from the group consisting of an alkoxysilane compound and a phosphate-based acrylate such as phosphate acrylate, Examples of the silane compound include 3-glycidoxypropyl trimethoxysilane, KBM-403 (Shin-Etsu Co., USA), 3-glycidoxypropyl methyldimethoxysilane KBM-402), 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, KBM-303, 3-glycidoxypropylmethyldiethoxysilane (3- Glycidoxypropyl methyldiethoxysilane, KBE-402), 3-glycidoxypropyl triethoxysilane (KBE-403), and 3-methacryloxypropyl trimethoxysilane ane, KBM-503), and one or more of them can be used.
상기 부착력 증진제가 사용될 경우 그 함량은, 전체 잉크 조성물에 대하여 1 내지 5중량%, 바람직하게는 2 내지 4중량%로서, 상기 부착력 증진제의 함량이 1중량% 미만일 경우에는 기재와 인쇄층의 부착력이 저하될 수 있고, 5중량%를 초과할 경우에는 잉크의 안정성 및 경화감도가 저하될 수 있다.When the adhesion promoting agent is used, the content thereof is 1 to 5% by weight, preferably 2 to 4% by weight based on the total ink composition. When the content of the adhesion promoting agent is less than 1% by weight, And if it is more than 5% by weight, the stability and curing sensitivity of the ink may be deteriorated.
상기 계면활성제는 잉크의 표면장력을 조절하여 제팅(jetting)이 원활하게 일어나게 하며, 또한, 기재에서 잉크가 적절하게 퍼지도록 하는 것으로서, DIC(DaiNippon Ink & Chemicals)사의 Megafack F-444, F-475, F-478, F-479, F-484, F-550, F-552, F-553, F-555, F-570 및 RS-75, 또는 아사히가라스사의 Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141 및 S-145, 또는 스미토모스리엠사의 Fluorad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430 및 FC-4430, 또는 듀퐁사의 Zonyl FS-300, FSN, FSN-100 및 FSO, 또는 BYK사의 BYK-306, BYK-310, BYK-320, BYK-330, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-359, BYK-361N, BYK-381, BYK-370, BYK-371, BYK-378, BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK-UV3500, BYK-UV3530, BYK-UV3570, BYKETOL-AQ, BYK-DYNWET 800, BYK-SILCLEAN 3700 및 BYK-UV 3570, 또는 테고사의 Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370 및 Flow 425 등을 예시할 수 있으며, 이들로 이루어진 군으로부터 선택되는 것을 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.The surface active agent controls the surface tension of the ink to smoothly jetting the ink, and also allows the ink to properly spread on the substrate. The surfactant is commercially available from Dai Nippon Ink & Chemicals, Megafack F-444, F-475 , F-478, F-479, F-484, F-550, F-552, F-553, F-555, F-570 and RS-75, or Surflon S- , Fluorad FC-93, FC-95, FC-98, FC-129 and FC-135 of Sumitomo 3M, S-113, S-121, S-131, S- 310, BYK-320, BYK-320, BYK-330, BYK-300, FSN, FSN-100 and FSO from DuPont, 361, BYK-381, BYK-370, BYK-371, BYK-331, BYK-333, BYK-342, BYK-350, BYK-354, BYK-355, BYK- BYK-388, BYK-392, BYK-394, BYK-399, BYK-3440, BYK-3441, BYK-UV3500, BYK-UV3530, BYK-UV3570, BYKETOL-AQ, BYK-DYNWET 800, BYK -SILCLEAN 3700 and BYK-UV 3570, or Rad 2100, Rad 2011, Glide 100, Glide 410, Glide 450, Flow 370 and Flow 425, and the like, and those selected from the group consisting of these may be used singly or in combination of two or more.
상기 계면활성제가 잉크 조성물에 포함될 경우 그 함량은, 전체 잉크 조성물에 대하여 0.1 내지 5중량%, 바람직하게는 0.5 내지 3중량%이고, 상기 계면활성제의 함량이 0.1중량% 미만일 경우에는, 조성물의 표면장력을 낮추는 효과가 충분하지 않아 기재에 조성물을 코팅 시 코팅 불량 현상이 발생하게 되고, 5중량%를 초과할 경우에는, 계면활성제가 과량으로 사용되어 조성물의 상용성 및 소포성이 오히려 감소하게 되는 문제점이 발생할 수 있다.When the surfactant is included in the ink composition, the content thereof is 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total ink composition. When the content of the surfactant is less than 0.1% by weight, The effect of lowering the tensile force is insufficient and coating failure phenomenon occurs when the composition is coated on the substrate. When the amount of the surfactant is more than 5% by weight, the surfactant is used in an excess amount and the compatibility and defoaming property of the composition is rather reduced Problems may arise.
본 발명에서 사용하는 자외선 경화형 잉크 조성물은 잉크젯 프린팅 직후 짧은 시간 내에 퍼짐이 일어나서, 우수한 도막 특성을 나타내며, 경화되어 우수한 접착 특성을 나타낸다. 따라서, 상기 자외선 경화형 잉크 조성물을 적용시에는 잉크젯 프린팅과 동시에 경화가 가능하도록 잉크젯 헤드 바로 뒤에 UV 램프를 설치하는 것이 바람직하다. The ultraviolet curable ink composition used in the present invention spreads within a short time immediately after inkjet printing, exhibits excellent coating film characteristics, and exhibits excellent adhesion properties by curing. Accordingly, when the ultraviolet curable ink composition is applied, it is preferable to provide a UV lamp immediately after the inkjet head so that curing can be performed simultaneously with inkjet printing.
상기 자외선 경화형 잉크 조성물은 경화 도즈량이 1 내지 10,000mJ/㎠, 바람직하게는 1,000 내지 2,000mJ/㎠이다.The ultraviolet curable ink composition has a curing dose of 1 to 10,000 mJ / cm2, preferably 1,000 to 2,000 mJ / cm2.
상기 자외선 경화형 잉크 조성물은 250nm 내지 450nm, 바람직하게는 360nm 내지 410nm의 파장 범위에서 방사선을 흡수하여 경화된다.The ultraviolet curable ink composition is cured by absorbing radiation in a wavelength range of 250 to 450 nm, preferably 360 to 410 nm.
상기 자외선 경화형 잉크 조성물은 일 예로 25℃에서 1cP 내지 50cP, 더욱 바람직하게는 25℃에서 3cP 내지 45cP 이하의 점도를 가짐으로써 잉크젯 공정에 적합하다. 상기의 점도 범위를 갖는 자외선 경화형 잉크 조성물은 공정 온도에서의 토출이 양호하다. 상기 공정 온도는 경화형 잉크 조성물의 점도가 낮아지도록 가열한 온도를 의미한다. 공정 온도는 10℃ 내지 100℃일 수 있으며, 바람직하게는 20℃ 내지 70℃일 수 있다.The ultraviolet curable ink composition is suitable for an inkjet process, for example, by having a viscosity of 1 cP to 50 cP at 25 캜, more preferably 3 cP to 45 cP at 25 캜. The ultraviolet curable ink composition having the viscosity range described above has good ejection at the process temperature. The process temperature means a temperature at which the viscosity of the curable ink composition is lowered. The process temperature may be from 10 캜 to 100 캜, and preferably from 20 캜 to 70 캜.
상기 자외선 경화형 잉크 조성물은 기재에 대한 밀착력 및 코팅성이 우수하다.The ultraviolet curable ink composition has excellent adhesion to a substrate and coating property.
또한, 상기 자외선 경화형 잉크 조성물로 본 발명에 따라 형성한 베젤패턴은 기재에 대한 부착력이 우수하며, 후 공정(열처리)이 배제된 상태에서의 기재와의 부착력이 cross cut test 4B 이상이다.In addition, the bezel pattern formed according to the present invention with the ultraviolet ray curable ink composition is excellent in adhesion to a substrate, and the adhesive force with a substrate in a state where a post-process (heat treatment) is excluded is cross-cut test 4B or more.
다음으로, 본 발명에 따른 자외선 경화형 잉크 조성물을 이용한 베젤패턴의 형성방법에 대하여 설명한다. 상기 자외선 경화형 잉크 조성물을 이용한 베젤패턴의 형성방법은, a) 기판에 제1항에 따른 잉크젯용 자외선 경화 잉크 조성물을 잉크젯 프린팅하여, 베젤패턴을 형성하는 단계; 및 b) 상기 베젤패턴에 자외선을 조사하여 경화하는 단계를 포함한다. 여기서, 상기 경화된 베젤패턴의 두께는 2 내지 6㎛, 또는 2 내지 4㎛일 수 있고, 한편, 이에 대한 구체적인 설명은, 상기 잉크 조성물 항목에서 설명된 것과, 통상의 양이온 중합 잉크 조성물을 이용한 베젤패턴 형성방법에 준한다.Next, a method of forming a bezel pattern using the ultraviolet curable ink composition according to the present invention will be described. A method of forming a bezel pattern using the ultraviolet curable ink composition comprises the steps of: a) inkjet printing a UV curable ink composition for inkjet according to claim 1 on a substrate to form a bezel pattern; And b) curing the bezel pattern by irradiating ultraviolet light. Here, the thickness of the cured bezel pattern may be 2 to 6 占 퐉, or 2 to 4 占 퐉, and a detailed description thereof will be given in connection with the description of the ink composition item, the bezel using a conventional cationic polymerization ink composition It follows the pattern formation method.
한편, 본 발명은 상기 자외선 경화형 잉크 조성물을 사용하여 제조한, 또는, 상기 베젤패턴의 형성방법에 따라 제조한 베젤패턴을 제공한다.Meanwhile, the present invention provides a bezel pattern prepared using the ultraviolet curable ink composition or manufactured according to the method of forming the bezel pattern.
또한, 본 발명은 상기 베젤패턴을 포함하는 디스플레이 기판을 제공한다. 여기서, 상기 디스플레이는 플라즈마 디스플레이 패널(Plasma Display Panel, PDP), 발광 다이오드(Light Emitting Diode, LED), 유기 발광 소자(Organic Light Emitting Diode, OLED), 액정 표시 장치(Liquid Crystal Display, LCD), 박막 트랜지스터 액정 표시 장치(Thin Film Transistor-Liquid Crystal Display, LCD-TFT) 및 음극선관(Cathode Ray Tube, CRT) 중 어느 하나에 사용되는 것일 수 있다.The present invention also provides a display substrate including the bezel pattern. Here, the display may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display A liquid crystal display (LCD), a liquid crystal display (LCD), and a cathode ray tube (CRT).
또한, 본 발명에 따른 블랙 베젤패턴은 폴더블 디스플레이의 커버윈도우에 포함되는 투명 PI 필름이나 하드 코팅층에 형성되며, 얇은 두께에서 차광 특성이 우수하여 패널의 패턴 시인성 및 단차 시인 문제가 발생하지 않는다. 1도 인쇄로 UV경화하면 높은 차광특성(O.D 5)으로 인해 발생하는 표면주름은 자외선 반사율이 높은 광 확산제를 적용하여 억제하였으며, 장파장 설포늄 양이온 광 개시제를 적용하여 열 안정성 및 경화감도가 우수하다. 본 발명의 조성물은 2도 인쇄도 가능하지만 커버윈도우 필름에 1도 인쇄로 베젤패턴을 형성하면 2도 인쇄 시 필요로 하는 얼라인먼트(alignment)가 없어도 되므로 공정 시간 및 비용(수율)을 개선할 수 있다.Also, the black bezel pattern according to the present invention is formed on the transparent PI film or the hard coating layer included in the cover window of the foldable display, and has excellent light shielding property at a thin thickness, so that the visibility of the panel and the problem of step difference are not generated. The surface wrinkles caused by the high shading property (OD 5) were suppressed by applying a light diffusing agent having a high ultraviolet reflectance when the UV curing was performed by printing at 1 degree, and the long-wavelength sulfonium cation photoinitiator was applied to improve heat stability and curing sensitivity Do. Although the composition of the present invention can be printed at 2 degrees, if a bezel pattern is formed on the cover window film by printing at 1 degree, there is no alignment required for printing at 2 degrees, which can improve the process time and cost (yield) .
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the appended claims. Such changes and modifications are intended to be within the scope of the appended claims.
실시예Example
[실시예 1] 자외선 경화형 잉크 조성물의 제조[Example 1] Preparation of UV curable ink composition
하기 표 1에 나타낸 조성과 같이, 전체 잉크 조성물 총 중량에 대하여, 안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 부틸 다이글라임(Butyl diglyme) 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 본 발명의 자외선 경화형 잉크 조성물을 제조하였다.(18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, and 30% by weight of butyl diglyme) relative to the total weight of the total ink composition as shown in the following Table 1, The UV curable ink composition of the present invention was prepared by stirring for 7 hours with a mixture of 7 wt% of CeLoxide 2021P, 25 wt% of oxetane OXT-221, 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) .
[실시예 2] 자외선 경화형 잉크 조성물의 제조[Example 2] Preparation of ultraviolet ray curable ink composition
하기 표 1에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 디에틸 석신산(Diethyl succinate) 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 본 발명의 자외선 경화형 잉크 조성물을 제조하였다.As shown in the following composition shown in Table 1, a pigment dispersion (18 wt% of carbon black, 5 wt% of TiO 2 , 4 wt% of dispersant, 30 wt% of diethyl succinate), 7 wt% of Celloxide 2021P, 25 wt% of cetane OXT-221, 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ultraviolet curable ink composition of the present invention.
[실시예 3] 자외선 경화형 잉크 조성물의 제조[Example 3] Preparation of UV curable ink composition
하기 표 1에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, Al 2O 3 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 본 발명의 자외선 경화형 잉크 조성물을 제조하였다.(18% by weight of carbon black, 5% by weight of Al 2 O 3 , 4% by weight of dispersant, 30% by weight of diethylsuccinic acid), 7% by weight of Celloxide 2021P, 10% by weight of oxetane OXT 221, 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ultraviolet curable ink composition of the present invention.
[실시예 4] 자외선 경화형 잉크 조성물의 제조[Example 4] Preparation of UV curable ink composition
하기 표 1에 나타낸 조성과 같이, 안료분산액(카본블랙 15중량%, TiO 2 5중량%, 분산제 3.5중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 28.5중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 본 발명의 자외선 경화형 잉크 조성물을 제조하였다.(15% by weight of carbon black, 5% by weight of TiO 2 , 3.5% by weight of dispersant and 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 10% by weight of oxetane OXT-221 28.5% by weight of KBM-403, 2% by weight of KBM-403, 3% by weight of a photoinitiator (Omnicat 550) and 6% by weight of GBL were stirred and mixed for 5 hours to prepare an ultraviolet curable ink composition of the present invention.
Figure PCTKR2018015664-appb-img-000001
Figure PCTKR2018015664-appb-img-000001
* 셀록사이드 2021P: (3',4'-에폭시사이클로헥산)메틸 3,4-에폭시사이클로헥실카복실레이트* Celloxide 2021P: (3 ', 4'-epoxycyclohexane) Methyl 3,4-epoxycyclohexyl carboxylate
* OXT-221: 비스[1-에틸(3-옥세타닐)]메틸에테르* OXT-221: bis [1-ethyl (3-oxetanyl)] methyl ether
* KBM-403: 3-글리시독시프로필 트리메톡시실란KBM-403: 3-glycidoxypropyltrimethoxysilane
* Omnicat 550: 10-[1,1'-바이페닐]-4-일-2-(1-메틸에틸)-9-옥소-9H-티오크산테늄 헥사플루오로포스페이트* Omnicat 550: 10- [1,1'-biphenyl] -4-yl-2- (1-methylethyl) -9-oxo-9H-thioxanetetanium hexafluorophosphate
[비교예 1] 잉크 조성물의 제조[Comparative Example 1] Preparation of ink composition
하기 표 2에 나타낸 조성과 같이, 안료분산액(카본블랙 12중량%, TiO 2 5중량%, 분산제 3중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 32중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.( 2 % by weight of carbon black, 5% by weight of TiO 2 , 3% by weight of dispersant, 30% by weight of diethylsuccinic acid), 7% by weight of Celloxide 2021P, 10% by weight of oxetane OXT-221 32% by weight of KBM-403, 2% by weight of KBM-403, 3% by weight of a photoinitiator (Omnicat 550) and 6% by weight of GBL for 5 hours.
[비교예 2] 잉크 조성물의 제조[Comparative Example 2] Preparation of ink composition
하기 표 2에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, SiO 2 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.(18% by weight of carbon black, 5% by weight of SiO 2 , 4% by weight of dispersant and 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 10% by weight of oxetane OXT-221 25% by weight of KBM-403, 2% by weight of KBM-403, 3% by weight of a photoinitiator (Omnicat 550) and 6% by weight of GBL were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 3] 잉크 조성물의 제조[Comparative Example 3] Preparation of ink composition
하기 표 2에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 30중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.(18% by weight of carbon black, 4% by weight of dispersant, 30% by weight of diethylsuccinic acid), 7% by weight of Celloxide 2021P, 30% by weight of oxetane OXT-221, 100% by weight of KBM- 2% by weight of 403, 3% by weight of a photoinitiator (Omnicat 550) and 6% by weight of GBL were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 4] 잉크 조성물의 제조[Comparative Example 4] Preparation of ink composition
하기 표 2에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, TiO 2 3중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 27중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.(18% by weight of carbon black, 3% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 10% by weight of oxetane OXT-221 27% by weight of KBM-403, 2% by weight of KBM-403, 3% by weight of a photoinitiator (Omnicat 550) and 6% by weight of GBL were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 5] 잉크 조성물의 제조[Comparative Example 5] Preparation of ink composition
하기 표 2에 나타낸 조성과 같이, 안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, BCsA 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.(5% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant and 30% by weight of BCSA), 7% by weight of Celloxide 2021P, 25% by weight of oxetane OXT- 2 wt% of KBM-403, 3 wt% of a photoinitiator (Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 6] 잉크 조성물의 제조[Comparative Example 6] Preparation of ink composition
안료분산액(카본블랙 18중량%, TiO2 5중량%, 분산제 4중량%, BCA 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(Omnicat 550) 3중량% 및 GBL 6중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.Pigment dispersion (18 wt% carbon black, 5 wt% TiO2, 4 wt% dispersant, 30 wt% BCA), 7 wt% of Celloxide 20P, 25 wt% of oxetane OXT-221, 2 wt% of KBM- Omnicat 550) and 6 wt% of GBL were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 7] 잉크 조성물의 제조[Comparative Example 7] Preparation of ink composition
안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 29중량%, KBM-403 2중량%, 광개시제(CPI-210S) 4중량% 및 증감제 (DBA) 1중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (CPI-210S) and 1% by weight of a sensitizer (DBA) were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 8] 잉크 조성물의 제조[Comparative Example 8] Preparation of ink composition
안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 25중량%, KBM-403 2중량%, 광개시제(UV692S) 4중량%, GBL 4중량% 및 증감제 (DBA) 1중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 25% by weight of oxetane OXT- , 4% by weight of a photoinitiator (UV692S), 4% by weight of GBL and 1% by weight of a sensitizer (DBA) for 5 hours to prepare an ink composition.
[비교예 9] 잉크 조성물의 제조[Comparative Example 9] Preparation of ink composition
안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 29중량%, KBM-403 2중량%, 광개시제(Irgacure 290) 4중량% 및 증감제(DBA) 1중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (Irgacure 290) and 1% by weight of a sensitizer (DBA) were stirred and mixed for 5 hours to prepare an ink composition.
[비교예 10] 잉크 조성물의 제조[Comparative Example 10] Preparation of ink composition
안료분산액(카본블랙 18중량%, TiO 2 5중량%, 분산제 4중량%, 디에틸 석신산 30중량%), 셀록사이드 2021P 7중량%, 옥세탄 OXT-221 29중량%, KBM-403 2중량%, 광개시제(Irgacure 250) 4중량% 및 증감제(ITX) 1중량%를 5시간 동안 교반 혼합하여 잉크 조성물을 제조하였다.Pigment dispersion (18% by weight of carbon black, 5% by weight of TiO 2 , 4% by weight of dispersant, 30% by weight of diethyl succinic acid), 7% by weight of Celloxide 2021P, 29% by weight of oxetane OXT- , 4% by weight of a photoinitiator (Irgacure 250) and 1% by weight of a sensitizer (ITX) were stirred and mixed for 5 hours to prepare an ink composition.
Figure PCTKR2018015664-appb-img-000002
Figure PCTKR2018015664-appb-img-000002
* 셀록사이드 2021P: (3',4'-에폭시사이클로헥산)메틸 3,4-에폭시사이클로헥실카복실레이트* Celloxide 2021P: (3 ', 4'-epoxycyclohexane) Methyl 3,4-epoxycyclohexyl carboxylate
* OXT-221: 비스[1-에틸(3-옥세타닐)]메틸에테르* OXT-221: bis [1-ethyl (3-oxetanyl)] methyl ether
* KBM-403: 3-글리시독시프로필 트리메톡시실란KBM-403: 3-glycidoxypropyltrimethoxysilane
* Omnicat 550: 10-[1,1'-바이페닐]-4-일-2-(1-메틸에틸)-9-옥소-9H-티오크산테늄 헥사플루오로포스페이트* Omnicat 550: 10- [1,1'-biphenyl] -4-yl-2- (1-methylethyl) -9-oxo-9H-thioxanetetanium hexafluorophosphate
* CPI-210S: 4-(페닐티오)페닐디페닐술포늄 트리스(펜타플루오로에틸)트리플루오로에틸)트리플루오로포스페이트CPI-210S: 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluoroethyl) trifluorophosphate
* UV-692S: 디페닐(4-(페닐티오)페닐)설포늄 헥사플루오로안티모네이트 (Diphenyl(4-(phenylthio)phenyl)sulfonium hexafluoroantimonate)* UV-692S: Diphenyl (4- (phenylthio) phenyl) sulfonium hexafluoroantimonate: diphenyl (4- (phenylthio) phenyl) sulfonium hexafluoroantimonate
* Irgacure 290: 테트랄리스(2,3,4,5,6-펜타플루오로페닐)보라누이드; 트리스[4-(4-아세틸페닐)설파닐페닐]설포늄(tetralis(2,3,4,5,6-pentafluorophenyl)boranuide; tris[4-(4-acetylphenyl)sulfanylphenyl]sulfonium) * Irgacure 290: tetralis (2,3,4,5,6-pentafluorophenyl) boranoid; Tris [4- (4-acetylphenyl) sulfanylphenyl] sulfonium (Tris [4- (4-acetylphenyl) sulfanylphenyl]
* Irgacure 250: 프로필렌 카보네이트 중의 요오도늄, (4-메틸페닐)[4-(2-메틸프로필)페닐]-, 헥사플루오로포스페이트(1-)의 75% 용액(75% solution of Iodonium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-, hexafluorophosphate(1-) in propylene carbonate)Irgacure 250: 75% solution of iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl], hexafluorophosphate (1-) in propylene carbonate (75% solution of Iodonium, -methylphenyl) [4- (2-methylpropyl) phenyl] -, hexafluorophosphate (1) in propylene carbonate)
* GBL: 감마부티로락톤* GBL: gamma butyrolactone
* ITX: 2-이소프로필티오크산톤(2-isopropylthioxanthone)* ITX: 2-isopropylthioxanthone (2-isopropylthioxanthone)
* DBA: 9,10-디부톡시안트라센(9,10-Dibutoxyanthracene)* DBA: 9,10-Dibutoxyanthracene (9,10-dibutoxyanthracene)
[시험예] 잉크 조성물로 제조된 시편의 물성 평가[Test Example] Evaluation of physical properties of a specimen made of an ink composition
상기 실시예 1 내지 4 및 비교예 1 내지 10에서 제조된 잉크 조성물을, 하드코팅 필름 기재 상에, X-rite 341C를 이용하여 광학밀도(O.D) 5로 잉크젯 프린팅하여 시편(sample)을 제작한 후, 시편의 인쇄두께, 경화감도, 부착력, 잉크젯 공정성(idle time), 표면주름 및 저장 안정성을 평가하였으며, 그 결과를 하기 표 3 및 4에 나타내었다.The ink compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 10 were ink-jet printed on a hardcoat film substrate at an optical density (OD) of 5 using X-rite 341C to prepare a sample The print thickness, curing sensitivity, adhesion, ink jet idle time, surface wrinkle and storage stability of the test pieces were evaluated. The results are shown in Tables 3 and 4 below.
여기서, 경화감도는 395㎚ 파장의 UV LED 램프를 이용하여 점착력이 없어지는 지점(tack free point)에서 UV 에너지를 확인하였고, 부착력은 cross cut test로 측정하여 0B 내지 5B로 평가하였으며(규격: ASTM D3002, D3359), 잉크젯 공정성은 전 노즐이 나오는 상태에서 Short purse(3s) 및 와이핑(wiping) 후 휴지시간(idle time)에 따른 젯팅(jetting) 평가로 확인하였고, 표면주름은 UV 경화 후 표면주름 여부를 육안으로 확인하였고, 저장 안정성은 잉크를 45℃ 오븐에 보관하여 1주 경과 후 점도가 증가된 정도가 10% 이하인지 여부를 확인하였다.Here, the curing sensitivity was evaluated by measuring the UV energy at a tack free point at which the adhesive strength was lost using a UV LED lamp having a wavelength of 395 nm, and the adhesion was evaluated as 0B to 5B by a cross cut test (standard: ASTM D3002, D3359), inkjet processability was confirmed by jetting evaluation according to idle time after short purse (3s) and wiping with all nozzles out, Whether the wrinkles were wrinkled or not was visually confirmed. The storage stability of the ink was confirmed by storing the ink in an oven at 45 ° C for less than 10% after one week.
Figure PCTKR2018015664-appb-img-000003
Figure PCTKR2018015664-appb-img-000003
Figure PCTKR2018015664-appb-img-000004
Figure PCTKR2018015664-appb-img-000004
상기 표 3 및 4의 결과로부터, 본 발명에 따른 실시예 1 내지 4의 조성물은 경화감도, 부착력, 잉크젯 공정성, 저장 안정성이 우수하고, 표면주름이 발생하지 않아, 신뢰성에 문제 없고 본 발명에 적합하였음을 확인할 수 있었다.이에 반해, 비교예 1의 조성물은 실시예 2에서 카본블랙 함량을 12%로 낮춘 조성으로 베젤 두께가 5㎛로 높아지면서 신뢰성 문제가 발생하였고, 비교예 2의 조성물은 실시예 2에서 광확산제를 SiO 2 5%로 변경한 잉크로 표면주름이 발생하였고, 비교예 3의 조성물은 실시예 2에서 광확산제를 제거한 잉크로 표면주름이 발생하였고, 비교예 4의 조성물은 실시예 2에서 광확산제 TiO 2의 함량을 3%로 낮춘 잉크로 표면주름이 발생하였다. 또, 비교예 5의 조성물은 실시예 1에서 용매를 BCsA로 변경한 잉크로 잉크젯 공정성 1분 이하로 나빠졌고, 비교예 6의 조성물은 실시예 1에서 용매를 BCA로 변경한 잉크로 경화감도(20,000mJ/㎠)가 좋지 않았다. 또한, 비교예 7의 조성물은 실시예 2에서 광중합 개시제를 CPI-210S로 변경한 잉크로 경화감도(10,000mJ/㎠)가 좋지 않았고, 비교예 8의 조성물은 실시예 2에서 광중합 개시제를 UV-692S로 변경한 잉크로 경화감도(12,000mJ/㎠)가 좋지 않았고, 비교예 9의 조성물은 실시예 2에서 광중합 개시제를 Irgacure 290으로 변경한 잉크로 경화감도(15,000mJ/㎠)가 좋지 않았고, 비교예 10의 조성물은 실시예 2에서 광중합 개시제를 Irgacure 250으로 변경한 잉크로 경화감도(6,000mJ/㎠)는 좋지만, 저장 안정성(45℃ 1주 보관, 점도 상승 10% 이상)이 좋지 않았다.From the results of Tables 3 and 4, it can be seen that the compositions of Examples 1 to 4 according to the present invention are excellent in curing sensitivity, adhesive force, inkjet processability and storage stability, On the contrary, the composition of Comparative Example 1 had a lowered carbon black content to 12% in Example 2, and the reliability of the bezel increased to 5 탆. In Example 2, surface wrinkles occurred in the ink in which the light diffusing agent was changed to 5% SiO 2. In Comparative Example 3, surface wrinkles occurred in the ink from which the light diffusing agent was removed in Example 2, and the composition of Comparative Example 4 Surface wrinkles occurred in the ink of Example 2 in which the content of the light diffusing agent TiO 2 was reduced to 3%. In addition, the composition of Comparative Example 5 was degraded to less than one minute in inkjet processability with the ink of Example 1 changed to BCSA, and the composition of Comparative Example 6 was cured with the ink of Example 1 in which the solvent was changed to BCA 20,000 mJ / cm 2) was not good. In addition, the composition of Comparative Example 7 had poor curing sensitivity (10,000 mJ / cm 2) in the ink in which the photopolymerization initiator was changed to CPI-210S in Example 2, and the composition of Comparative Example 8 had the UV- (12,000 mJ / cm < 2 >) was poor in the ink changed to 692S, and the composition of Comparative Example 9 had poor curing sensitivity (15,000 mJ / cm < 2 >) in the ink of Example 2 in which the photopolymerization initiator was changed to Irgacure 290, The composition of Comparative Example 10 was good in curing sensitivity (6,000 mJ / cm 2) with an ink prepared by changing the photopolymerization initiator to Irgacure 250 in Example 2, but the storage stability (45 ° C for one week storage, viscosity increase of 10% or more) was not good.
이상으로 본 발명 내용의 특정한 부분을 도면 및 실시예를 통해 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been particularly shown and described with reference to particular embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments, It will be clear that it is not. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

  1. 블랙 안료; 분산제; 에폭시 화합물; 옥세탄 화합물; 광확산제; 광중합 개시제; 및 유기 용매를 포함하는 블랙 베젤패턴 형성용 자외선 경화형 잉크 조성물.Black pigment; Dispersing agent; Epoxy compounds; Oxetane compounds; A light diffusing agent; A photopolymerization initiator; And an organic solvent.
  2. 제1항에 있어서, 상기 광확산제는 TiO 2 또는 Al 2O 3 또는 이의 조합을 포함하는 것인, 자외선 경화형 잉크 조성물.The UV curable ink composition according to claim 1, wherein the light diffusing agent comprises TiO 2 or Al 2 O 3 or a combination thereof.
  3. 제1항에 있어서, 상기 유기 용매는 비점이 200℃ 이상이고, 25℃에서 점도가 1cP 내지 5cP인 것인, 자외선 경화형 잉크 조성물.The UV curable ink composition according to claim 1, wherein the organic solvent has a boiling point of 200 ° C or higher and a viscosity of 1 cP to 5 cP at 25 ° C.
  4. 제1항에 있어서, 상기 광중합 개시제는 10-[1,1'-바이페닐]-4-일-2-(1-메틸에틸)-9-옥소-9H-티오크산테늄 헥사플루오로포스페이트(10-[1,1'-Biphenyl]-4-yl-2-(1-methylethyl)-9-oxo-9H-thioxanthenium hexafluorophosphate)인 것인, 자외선 경화형 잉크 조성물.The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator is at least one selected from the group consisting of 10- [1,1'-biphenyl] -4-yl-2- (1-methylethyl) -9-oxo-9H-thioxanetetanium hexafluorophosphate Wherein the UV curable ink composition is 10- [1,1'-Biphenyl] -4-yl-2- (1-methylethyl) -9-oxo-9H-thioxanthenium hexafluorophosphate.
  5. 제1항에 있어서, 상기 블랙 안료의 함량은 전체 잉크 조성물에 대하여 15 내지 20중량%인 것인, 자외선 경화형 잉크 조성물.The ultraviolet curable ink composition according to claim 1, wherein the content of the black pigment is 15 to 20% by weight based on the total ink composition.
  6. 제1항에 있어서, 상기 유기 용매의 함량은 전체 잉크 조성물에 대하여 20 내지 40중량%인 것인, 자외선 경화형 잉크 조성물.The ultraviolet curable ink composition according to claim 1, wherein the content of the organic solvent is 20 to 40% by weight based on the total ink composition.
  7. 제1항에 있어서, 점도가 25℃에서 1cP 내지 50cP이고, 경화 후 기재와의 부착력이 cross cut test 4B 이상인 것인, 자외선 경화형 잉크 조성물.The ultraviolet curable ink composition according to claim 1, wherein the viscosity is 1 cP to 50 cP at 25 캜, and the adhesion force with the substrate after curing is cross-cut test 4B or more.
  8. 제1항에 있어서, 경화 도즈량이 1000 내지 10,000mJ/㎠이고, 250nm 내지 410nm 파장 범위의 방사선을 흡수하여 경화되는 것인, 자외선 경화형 잉크 조성물.The ultraviolet curable ink composition according to claim 1, which has a curing dose of 1000 to 10,000 mJ / cm 2 and is cured by absorbing radiation in a wavelength range of 250 to 410 nm.
  9. a) 기판에 제1항에 따른 잉크젯용 자외선 경화형 잉크 조성물을 잉크젯 프린팅하여, 베젤패턴을 형성하는 단계; 및 a) ink-jet printing a UV curable ink composition for inkjet according to claim 1 on a substrate to form a bezel pattern; And
    b) 상기 베젤패턴에 자외선을 조사하여 경화하는 단계를 포함하는 베젤패턴의 형성방법.b) irradiating the bezel pattern with ultraviolet light to cure the bezel pattern.
  10. 제9항에 있어서, 상기 베젤패턴의 두께는 2 내지 4㎛인 것인, 베젤패턴의 형성방법.10. The method of claim 9, wherein the thickness of the bezel pattern is between 2 and 4 mu m.
  11. 제1항의 자외선 경화형 잉크 조성물을 사용하여 제조한 베젤패턴.A bezel pattern produced using the ultraviolet curable ink composition of claim 1.
  12. 제11항의 베젤패턴을 포함하는 디스플레이 기판.A display substrate comprising the bezel pattern of claim 11.
PCT/KR2018/015664 2017-12-14 2018-12-11 Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same WO2019117581A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880015062.6A CN110382640B (en) 2017-12-14 2018-12-11 Ultraviolet-curable black ink composition for foldable display and frame pattern forming method using the same
US16/492,811 US10858525B2 (en) 2017-12-14 2018-12-11 Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same
JP2019546930A JP6911274B2 (en) 2017-12-14 2018-12-11 UV curable black ink composition for foldable displays and bezel pattern forming method using it

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170171970 2017-12-14
KR10-2017-0171970 2017-12-14
KR10-2018-0157794 2018-12-10
KR1020180157794A KR102260090B1 (en) 2017-12-14 2018-12-10 UV-curable black ink composition for a foldable display and method of manufacturing a bezel pattern using the same

Publications (1)

Publication Number Publication Date
WO2019117581A1 true WO2019117581A1 (en) 2019-06-20

Family

ID=66819543

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/015664 WO2019117581A1 (en) 2017-12-14 2018-12-11 Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same

Country Status (1)

Country Link
WO (1) WO2019117581A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7977402B2 (en) * 2006-10-11 2011-07-12 Collins Ink Corporation Radiation curable inks
KR20150029921A (en) * 2013-09-11 2015-03-19 동우 화인켐 주식회사 A colored photosensitive resin composition for forming the frontal light-shielding layer of a display device
KR101537060B1 (en) * 2013-12-16 2015-07-15 한국신발피혁연구원 Ultraviolet―curable ink binder composition for light guide plate
KR20160037125A (en) * 2014-09-26 2016-04-05 주식회사 엘지화학 Uv-curable ink composition, manufacturing method for bezel pattern of display panel and bezel pattern of display panel using the same
KR20170098353A (en) * 2016-02-19 2017-08-30 삼성디스플레이 주식회사 Flexible display device, method for fabricating window member of the same, hard coating composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7977402B2 (en) * 2006-10-11 2011-07-12 Collins Ink Corporation Radiation curable inks
KR20150029921A (en) * 2013-09-11 2015-03-19 동우 화인켐 주식회사 A colored photosensitive resin composition for forming the frontal light-shielding layer of a display device
KR101537060B1 (en) * 2013-12-16 2015-07-15 한국신발피혁연구원 Ultraviolet―curable ink binder composition for light guide plate
KR20160037125A (en) * 2014-09-26 2016-04-05 주식회사 엘지화학 Uv-curable ink composition, manufacturing method for bezel pattern of display panel and bezel pattern of display panel using the same
KR20170098353A (en) * 2016-02-19 2017-08-30 삼성디스플레이 주식회사 Flexible display device, method for fabricating window member of the same, hard coating composition

Similar Documents

Publication Publication Date Title
CN107001825B (en) Ultraviolet-curable ink composition, method for manufacturing frame pattern of display substrate using same, and frame pattern manufactured thereby
US11760891B2 (en) Infrared ray transmittance ink composition for inkjet, method for preparing a bezel pattern using the same, the bezel pattern using the same method and display panel comprising the bezel pattern
WO2018110849A2 (en) Waveguide having light shielding film formed thereon and manufacturing method therefor
WO2016093672A1 (en) Photosensitive colored ink composition for bezel, bezel pattern formed by using same, and display substrate containing same
US11332631B2 (en) Film-printable ultraviolet-ray-curable ink composition, bezel pattern manufacturing method using same, bezel pattern manufactured according to same, and display substrate including same
CN110402275B (en) Ultraviolet-curable ink composition, method of manufacturing bezel pattern in display substrate using the same, and bezel pattern manufactured thereby
WO2019103415A1 (en) Waveguide tube including light-shielding film and method for manufacturing same
US10858525B2 (en) Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same
WO2018111043A1 (en) Photopolymerizable composition for forming bezel pattern, method for manufacturing bezel pattern of display substrate using same, bezel pattern manufactured thereby
US11485866B2 (en) Film-printable UV-curable ink composition, method for producing bezel pattern using same, bezel pattern produced by same, and foldable display substrate comprising same
WO2019117581A1 (en) Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same
WO2016048115A1 (en) Uv-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby
US10934443B2 (en) Infrared transmitting ink composition for ink jet, method for forming bezel pattern by using same, bezel pattern formed thereby, and display substrate comprising same
WO2019035595A1 (en) Infrared transmitting ink composition for ink jet, method for forming bezel pattern by using same, bezel pattern formed thereby, and display substrate comprising same
WO2016048117A1 (en) Uv-curable ink composition, method for producing bezel pattern of display substrate using same, and bezel pattern produced thereby
KR20210023503A (en) Photopolymerizable composition for forming bezel pattern, method of manufacturing bezel pattern by using the same, and bezel pattern prepared by using the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18888539

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019546930

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18888539

Country of ref document: EP

Kind code of ref document: A1