WO2019117581A1 - Composition d'encre noire durcissable aux ultraviolets pour afficheur pliable et procédé de formation de motif d'encadrement l'utilisant - Google Patents

Composition d'encre noire durcissable aux ultraviolets pour afficheur pliable et procédé de formation de motif d'encadrement l'utilisant 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
English (en)
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/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880015062.6A priority Critical patent/CN110382640B/zh
Priority to JP2019546930A priority patent/JP6911274B2/ja
Priority to US16/492,811 priority patent/US10858525B2/en
Publication of WO2019117581A1 publication Critical patent/WO2019117581A1/fr

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

La présente invention concerne une composition d'encre noire durcissable aux ultraviolets, un procédé de formation de motif d'encadrement l'utilisant, un motif d'encadrement produit par le procédé et un substrat d'affichage comprenant le motif d'encadrement, la composition d'encre noire durcissable aux ultraviolets étant une encre d'encadrement noire développée pour être appliquée à un film de fenêtre de couverture d'un afficheur pliable, ayant d'excellentes propriétés de protection contre la lumière et des propriétés de pliage à une épaisseur mince et, étant donné qu'un agent de diffusion de lumière est appliqué à l'encre, empêchant les rides de surface de se produire du fait d'une différence du taux de durcissement des parties supérieure et inférieure d'un encadrement, au moyen d'un durcissement par UV seul, sans processus de prétraitement.
PCT/KR2018/015664 2017-12-14 2018-12-11 Composition d'encre noire durcissable aux ultraviolets pour afficheur pliable et procédé de formation de motif d'encadrement l'utilisant WO2019117581A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880015062.6A CN110382640B (zh) 2017-12-14 2018-12-11 用于可折叠显示器的可紫外线固化的黑色油墨组合物和使用其的边框图案形成方法
JP2019546930A JP6911274B2 (ja) 2017-12-14 2018-12-11 フォルダブルディスプレイの紫外線硬化型ブラックインク組成物及びそれを用いたベゼルパターンの形成方法
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

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0171970 2017-12-14
KR20170171970 2017-12-14
KR1020180157794A KR102260090B1 (ko) 2017-12-14 2018-12-10 폴더블 디스플레이의 자외선 경화형 블랙 잉크 조성물 및 이를 이용한 베젤패턴의 형성방법
KR10-2018-0157794 2018-12-10

Publications (1)

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

Family

ID=66819543

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2018/015664 WO2019117581A1 (fr) 2017-12-14 2018-12-11 Composition d'encre noire durcissable aux ultraviolets pour afficheur pliable et procédé de formation de motif d'encadrement l'utilisant

Country Status (1)

Country Link
WO (1) WO2019117581A1 (fr)

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 (ko) * 2013-09-11 2015-03-19 동우 화인켐 주식회사 디스플레이 장치의 전면 차광층 형성용 착색 감광성 수지 조성물
KR101537060B1 (ko) * 2013-12-16 2015-07-15 한국신발피혁연구원 Ｕｖ 경화형 도광판 잉크 바인더용 조성물
KR20160037125A (ko) * 2014-09-26 2016-04-05 주식회사 엘지화학 자외선 경화형 잉크 조성물, 이를 이용한 디스플레이 기판의 베젤 패턴의 제조방법 및 이에 의하여 제조된 베젤 패턴
KR20170098353A (ko) * 2016-02-19 2017-08-30 삼성디스플레이 주식회사 플렉서블 표시장치, 윈도우 부재의 제조방법 및 하드 코팅 조성물

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 (ko) * 2013-09-11 2015-03-19 동우 화인켐 주식회사 디스플레이 장치의 전면 차광층 형성용 착색 감광성 수지 조성물
KR101537060B1 (ko) * 2013-12-16 2015-07-15 한국신발피혁연구원 Ｕｖ 경화형 도광판 잉크 바인더용 조성물
KR20160037125A (ko) * 2014-09-26 2016-04-05 주식회사 엘지화학 자외선 경화형 잉크 조성물, 이를 이용한 디스플레이 기판의 베젤 패턴의 제조방법 및 이에 의하여 제조된 베젤 패턴
KR20170098353A (ko) * 2016-02-19 2017-08-30 삼성디스플레이 주식회사 플렉서블 표시장치, 윈도우 부재의 제조방법 및 하드 코팅 조성물

Similar Documents

Publication Publication Date Title
CN107001825B (zh) 可紫外光固化的油墨组合物、使用其制造显示基板的边框图案的方法以及制造的边框图案
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 (fr) Guide d'ondes sur lequel est formé un film de protection contre la lumière et procédé de fabrication correspondant
WO2016093672A1 (fr) Composition d'encre de couleur photosensible pour contour d'écran, motif de contour d'écran formé à l'aide de celle-ci et substrat d'afficheur le comprenant
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 (zh) 可紫外线固化的油墨组合物、使用其制造显示基板中边框图案的方法和由此制造的边框图案
WO2019103415A1 (fr) Tube guide d'ondes comprenant un film de protection contre la lumière et son procédé de fabrication
US10858525B2 (en) Ultraviolet curable black ink composition for foldable display and bezel pattern forming method using same
WO2018111043A1 (fr) Composition photopolymérisable pour former un motif de cadre, procédé de fabrication de motif de cadre de substrat d'affichage l'utilisant, motif de cadre ainsi fabriqué
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 (fr) Composition d'encre noire durcissable aux ultraviolets pour afficheur pliable et procédé de formation de motif d'encadrement l'utilisant
WO2016048115A1 (fr) Composition d'encre durcissable par uv, procédé de production d'un motif de cadre pour substrat d'affichage l'utilisant, et motif de cadre ainsi produit
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 (fr) Composition d'encre transmettant les infrarouges pour jet d'encre, procédé de formation d'un motif en couronne faisant intervenir ladite composition, motif en couronne ainsi formé, et substrat d'affichage comprenant ledit motif
WO2016048117A1 (fr) Composition d'encre durcissable par uv, procédé de production d'un motif de cadre pour substrat d'affichage l'utilisant, et motif de cadre ainsi produit
KR20210023503A (ko) 베젤패턴 형성용 광중합성 조성물, 이를 이용한 베젤패턴의 형성방법 및 이에 의해 제조된 베젤패턴

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