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WO2021125695A1 - Composition durcissable pour impression à jet d'encre, et dispositif d'affichage électroluminescent organique la comprenant - Google Patents

Composition durcissable pour impression à jet d'encre, et dispositif d'affichage électroluminescent organique la comprenant Download PDF

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Publication number
WO2021125695A1
WO2021125695A1 PCT/KR2020/018112 KR2020018112W WO2021125695A1 WO 2021125695 A1 WO2021125695 A1 WO 2021125695A1 KR 2020018112 W KR2020018112 W KR 2020018112W WO 2021125695 A1 WO2021125695 A1 WO 2021125695A1
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WIPO (PCT)
Prior art keywords
meth
acrylate
curable composition
inkjet
oligomer
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PCT/KR2020/018112
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English (en)
Korean (ko)
Inventor
이주형
박한성
Original Assignee
주식회사 두산
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Publication of WO2021125695A1 publication Critical patent/WO2021125695A1/fr

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    • 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
    • C09D11/02—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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a curable composition for inkjet and an organic light emitting display device including the same, and more specifically, a reinforcing part having excellent modulus properties, flexibility and adhesion is formed under the display panel of the organic light emitting display through direct coating such as inkjet printing. It relates to a curable composition for inkjet and a display device including the same.
  • the flat panel display device examples include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescence display device.
  • the organic light emitting display device is a self-luminous display device that displays an image including an organic light emitting diode, and has high visibility due to self-luminescence, low power consumption, high luminance, and high response speed. Because of its characteristics, it is currently attracting attention as a display device.
  • the flat panel display device uses a glass substrate due to high heat generated during the manufacturing process, and thus there is a limit to light weight, thinness, and flexibility.
  • a flexible display apparatus capable of bending a screen by using a flexible plastic substrate instead of a non-flexible glass substrate is being developed as a next-generation flat panel display apparatus.
  • a back plate film composed of a polyethylene terephthalate (PET) substrate or polyimide (PI) substrate and an adhesive layer is attached to the lower portion of the flexible substrate.
  • PET polyethylene terephthalate
  • PI polyimide
  • a non-active area (N/A) ) to the back side of the display area is being considered.
  • a process of cutting and removing a portion of the backplate film corresponding to the area was required.
  • the backplate film had a cloudiness phenomenon during repeated folding of the flexible substrate.
  • An object of the present invention is to provide a curable composition for inkjet that can directly form a reinforcing part having excellent modulus properties, flexibility and adhesion under a display panel of an organic light emitting display device through direct coating such as inkjet printing.
  • Another object of the present invention is to provide an organic light emitting display device having excellent durability and lifespan characteristics by including a reinforcing part formed by directly coating the aforementioned curable composition for inkjet.
  • Another object of the present invention is to provide a method of manufacturing an organic light emitting display device having excellent efficiency, productivity, and cost reduction effects of a module process by directly coating the above-described curable composition to form a reinforcing part.
  • the present invention has a viscosity of 10 to 40 cPs and a surface tension of 18 to 40 dyne / cm under 25 ° C.
  • the cured product of the curable composition is measured according to ASTM D3330 at 25 ° C. provides an inkjet curable composition having an adhesive force of 150 gf/inch or more to an adherend, and a Young's modulus of 20 to 500 MPa at 25°C.
  • the present invention (a) a flexible substrate; a driving circuit unit disposed on one surface of the flexible substrate; and a display panel including an organic light emitting element part electrically connected to the driving circuit part, and (b) a reinforcement part disposed on the other surface of the flexible substrate and formed by directly coating the curable composition for inkjet.
  • Part provides an organic light emitting display device, wherein the adhesive force to the flexible substrate at 25°C measured according to ASTM D3330 is 150 gf/inch or more, and the Young's modulus at 25°C is 20 to 500 MPa.
  • the present invention comprises the steps of forming a flexible substrate on a carrier substrate; forming a driving circuit unit and an organic light emitting device unit on one surface of the flexible substrate, respectively; forming a thin film encapsulation unit on the organic light emitting device unit; laminating a process protective film on the thin film encapsulation unit; separating the carrier substrate; and directly coating the aforementioned curable composition for inkjet on the other surface of the flexible substrate to form a reinforcing part.
  • the curable composition for inkjet according to the present invention has excellent straightness, uniformity, and precision of the formed pattern, and can minimize the clogging of the inkjet head outlet and the aggregation of the pattern immediately after printing.
  • the cured product has excellent heat resistance, adhesion (adhesion) and modulus properties. Therefore, when the cured product of the curable composition according to the present invention is applied as a reinforcement part under the display panel in the organic light emitting display device, the flexible substrate of the display panel is stably supported and reinforced to improve the durability and lifespan characteristics of the organic light emitting display device. In addition, it is possible to implement flexibility and large-area of the organic light emitting display device.
  • the curable composition according to the present invention can directly form the reinforcing part under the display panel in the organic light emitting display device through a direct coating method such as inkjet printing, the efficiency, productivity, and cost reduction effect of the module process during manufacturing are improved. can be In addition, since the curable composition according to the present invention can be selectively coated only on the part where the reinforcing part is required, a free design can be implemented.
  • FIG. 1 is a cross-sectional view schematically illustrating an organic light emitting display device according to the present invention.
  • FIG. 2 is a plan view illustrating a state in which the flexible substrate of the organic light emitting diode display according to the present invention is not bent.
  • FIG. 3 is an enlarged cross-sectional view illustrating a cross section of a square ( ⁇ ) portion indicated by a broken line in FIG. 1 .
  • 4 to 10 are cross-sectional views illustrating each step of manufacturing the organic light emitting display device of the present invention.
  • 100 a display panel
  • 110 a flexible substrate
  • 141 a first electrode
  • 142 a light emitting layer
  • 143 a second electrode
  • 150 a gate insulating film
  • (meth) acrylate represents acrylate or methacrylate
  • (meth) acryl represents acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl .
  • a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less.
  • the "polymerizable functional group” is a group involved in the polymerization reaction, for example, may be a (meth)acrylate group.
  • the glass transition temperature of the A monomer is a theoretical value, and means the glass transition temperature (Tg) of the homopolymer made of the A monomer.
  • the curable composition for inkjet according to the present invention (hereinafter, 'curable composition') is a composition that undergoes photopolymerization by ultraviolet (UV) irradiation, and forms a reinforcing layer capable of supporting and reinforcing the flexible substrate of the display panel in the organic light emitting display device. can do.
  • UV ultraviolet
  • the curable composition is directly coated on a flexible substrate (eg, polyimide substrate) through a direct coating method such as inkjet printing (specifically, a non-contact direct coating method), as well as selectively coating only a necessary area.
  • a direct coating method such as inkjet printing (specifically, a non-contact direct coating method)
  • the surface tension is controlled in the range of about 18 to 40 dyne/cm. If the surface tension of the curable composition is less than about 18 dyne / cm or the viscosity of the curable composition is less than about 10 cPs, the curable composition may have poor straightness when counting or ejecting from the nozzle of the inkjet printing machine. .
  • the viscosity of the curable composition is greater than about 40 cPs or the surface tension is greater than about 40 dyne/cm, it may not be smoothly discharged from the nozzle.
  • the cured product of this curable composition has an adhesive force of at least about 150 gf/inch to an adherend (eg, a polyimide substrate) at 25° C. measured according to ASTM 3330, and a Young’s modulus of about 20 to 500 MPa at 25° C. has
  • the cured product of the curable composition may have a Young's modulus of 20 to 800 MPa measured at about 25° C. after standing for about 24 hours under conditions of about 85° C. and about 85%.
  • a cured product of such a curable composition may satisfy Relational Equation 1 below.
  • a reinforcing part having excellent high-temperature durability and lifespan characteristics may be formed on a display device through direct coating.
  • M 1 is the Young's modulus of the cured product measured at about 25 °C
  • M 2 is the Young's modulus of the cured product measured at about 25° C. after standing for about 24 hours under conditions of about 85° C. and about 85%).
  • the cured product of the curable composition may have a surface hardness in the range of about 2 to 20 MPa. As described above, the cured product of the curable composition has excellent impact resistance.
  • the cured product of the curable composition may have a thermal decomposition temperature of 3 wt% loss measured by thermogravimetric analysis (TGA) of about 180° C. or higher.
  • TGA thermogravimetric analysis
  • the cured product of the curable composition may form a reinforcing part having excellent heat resistance by directly coating the display device.
  • the curable composition according to the present invention has excellent straightness, uniformity, and precision of the formed pattern, and can minimize inkjet head outlet clogging and pattern aggregation immediately after printing.
  • the curable composition of the present invention can be easily cured even by a small amount of ultraviolet irradiation.
  • the curable composition of the present invention can be selectively coated directly on the base substrate of the display device only in the required region according to the folded region and the non-folded region to form a reinforcing part, unlike the conventional lower protective film, a process of cutting the film, etc. This is not necessary, and thus the manufacturing process of the display device can be simplified.
  • the curable composition according to the present invention since the curable composition according to the present invention has excellent impact resistance, bendability, and elasticity, a flexible display device having a large area can be manufactured. In addition, since the curable composition according to the present invention can selectively coat only necessary parts according to various folded and non-folded regions of the display device, it is possible to reduce manufacturing process costs and form reinforcement parts having various designs. have.
  • the curable composition of the present invention may include an oligomer containing at least one selected from the group consisting of a urethane (meth)acrylate oligomer and an epoxy (meth)arrylate oligomer; a reactive monomer containing at least one selected from the group consisting of a monofunctional (meth)acrylate monomer, a bifunctional (meth)acrylate monomer, and a polyfunctional (meth)acrylate monomer; and a photopolymerization initiator.
  • the oligomer may further contain a phosphate (meth)acrylate oligomer.
  • the reactive oligomer is a main component that forms a coating film after photopolymerization, and forms a crosslinked structure with the reactive monomer to control the modulus properties, flexibility, adhesiveness, etc. of the cured product.
  • oligomers may contain at least one selected from the group consisting of urethane (meth)acrylate oligomers and epoxy (meth)arrylate oligomers.
  • it may further contain a phosphate (meth)acrylate oligomer.
  • the oligomer may contain a urethane (meth)acrylate oligomer or an epoxy (meth)arrylate oligomer.
  • the oligomer may contain a urethane (meth)acrylate oligomer and a phosphate (meth)acrylate oligomer.
  • the urethane (meth)acrylate oligomer is a (meth)acrylate oligomer having an intramolecular urethane bond, and may be used without particular limitation as long as it is known in the art.
  • reaction product obtained by esterifying a polyurethane oligomer obtained by reaction of a polyol such as polybutadienediol, polyether polyol, polyester polyol, and polycarbonate diol with polyisocyanate with (meth)acrylic acid.
  • a polyol such as polybutadienediol, polyether polyol, polyester polyol, and polycarbonate diol with polyisocyanate with (meth)acrylic acid.
  • Examples of the aliphatic or aromatic diisocyanate include 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, cyclopentylene-1,3-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, iso Phorone diisocyanate, cyclohexene-1,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-methylenebis (phenyl isocyanate), 2,2-diphenylpropane- 4,4'-diisocyanate, p-phenylenediisocyanate, m-phenylenediisocyanate, xylenediisocyanate, 1,4-naphthylenediisocyanate, 1,5-naphthylenediisocyanate, 4,4'-diphenyldi isocyanate, azo
  • hydroxy (meth) acrylate monomer is not limited as long as it is generally known in the art, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, such as hydroxy (C 1 ⁇ C 12 ) alkyl (meth) acrylate ;
  • hydroxy (C 2 ⁇ C 12 ) alkylene glycol (meth) acrylate such as 2-hydroxyethylene glycol (meth) acrylate and 2-hydroxypropylene glycol (meth) acrylate, but is not limited thereto. . These may be used alone or in combination of two or more.
  • the urethane (meth)acrylate oligomer has at least 2 to 4 functional groups with a polymerizable functional group together with an intramolecular urethane bond (-NH-COO-). Accordingly, the urethane (meth)acrylate oligomer may have a viscosity of about 1,000 to 70,000 cPs at about 25° C., and specifically about 1,000 to 40,000 cPs.
  • the polymerizable functional group refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.
  • the urethane (meth)acrylate oligomer may have a weight average molecular weight (Mw) of about 100 to 30,000 g/mol.
  • Mw weight average molecular weight
  • the epoxy (meth)acrylate oligomer usable in the present invention is a (meth)acrylate oligomer containing an epoxy group in the molecule, for example, a novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type. and an oligomer obtained by reacting (meth)acrylic acid with an epoxy resin such as an epoxy resin.
  • the epoxy (meth) acrylate oligomer is a novolac epoxy (meth) acrylate oligomer, specifically, a group consisting of a phenol novolac epoxy (meth) acrylate oligomer and a cresol novolak type epoxy (meth) acrylate oligomer It may be one or more selected from.
  • Such an epoxy (meth)acrylate oligomer may have a viscosity at about 25° C. of about 1,000 to 70,000 cPs, and specifically about 1,000 to 40,000 cPs.
  • the epoxy (meth) acrylate oligomer is an oligomer having two or more (specifically, 2 to 4) functional groups of a polymerizable functional group together with an epoxy group in a molecule, and a weight average molecular weight (Mw) is about 1,000 to 50,000 g/mol.
  • the polymerizable functional group refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.
  • the phosphate (meth)acrylate oligomer usable in the present invention is an oligomer containing a phosphate group and an acrylate group in a molecule, and is not particularly limited as long as it is known in the art.
  • the phosphate (meth)acrylate oligomer is an oligomer of phosphate methacrylate.
  • the phosphate (meth)acrylate oligomer may have a weight average molecular weight (Mw) of about 500 to 2,000 g/mol, and a viscosity (about 25° C.) of about 500 to 3,500 cPs.
  • the acid value (acid value) of the phosphate (meth) acrylate oligomer may be about 200 to 400 mgKOH / g.
  • the content of the oligomer may be about 3 to 20 wt% based on the total amount of the photoreactive materials (ie, the oligomer and the reactive monomer) combined. That is, the ratio (mixing ratio) of the reactive monomer and the oligomer may be 80:20 to 97:3 by weight.
  • the adhesion of the cured product may be improved by appropriately adjusting the curing density, and physical properties such as impact resistance, bendability, and heat resistance may be improved.
  • the oligomer is a urethane (meth)acrylate oligomer
  • the content of the urethane (meth)acrylate oligomer is about 3 to 20% by weight based on the total amount of the total photoreactive material (ie, reactive monomer and oligomer).
  • the oligomer is an epoxy (meth)acrylate oligomer
  • the content of the epoxy (meth)acrylate oligomer is about 3 to 10% by weight based on the total amount of the total photoreactive material (ie, reactive monomer and oligomer).
  • the oligomer is at least one selected from the group consisting of urethane (meth) acrylate oligomer and epoxy (meth) acrylate oligomer; And when it contains a phosphate (meth)acrylate oligomer, the content of the phosphate (meth)acrylate oligomer is about 0.1 to 5% by weight based on the total amount of the total photoreactive material (ie, reactive monomer and oligomer). and the content of the urethane (meth)acrylate oligomer and/or the epoxy (meth)acrylate oligomer is about 3 to 20 wt% based on the total amount of the total photoreactive material (ie, the reactive monomer and the oligomer).
  • the photoreactive monomer is a main component for forming a coating film after photopolymerization, and is a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer. It contains at least one selected from the group consisting of.
  • the photoreactive monomer contains a monofunctional (meth)acrylate monomer, a bifunctional (meth)acrylate monomer, and a polyfunctional (meth)acrylate monomer.
  • the monofunctional (meth)acrylate monomer is a (meth)acrylate monomer having one polymerizable functional group that is an unsaturated group capable of polymerization.
  • the polymerizable functional group refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.
  • Monofunctional (meth)acrylate monomers usable in the present invention include C 1 to C 30 alkyl (meth) acrylate monomers, C 3 to C 30 alicyclic (meth) acrylate monomers, and 5 to 30 nuclear atoms.
  • the heteroalicyclic (meth)acrylate monomer and the heteroaromatic (meth)acrylate monomer may contain one or more heteroatoms selected from nitrogen, sulfur, and oxygen.
  • the monofunctional (meth)acrylate monomer is a C 1 to C 30 alkyl (meth) acrylate monomer, C 3 to C 30 alicyclic (meth) acrylate monomer, and 5 to 30 nuclear atoms. It may contain two or more selected from the group consisting of heteroalicyclic (meth)acrylate monomers.
  • the monofunctional (meth)acrylate monomer may further contain an epoxy mono(meth)acrylate.
  • the monofunctional (meth)acrylate monomer usable in the present invention include ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl acrylate, isopropyl acrylic rate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl acrylate, 2-ethylbutyl (meth)acrylate, nonyl (meth)acrylate [nonyl (meth)acrylate] , n-octyl (meth)acrylate, lauryl (meth)acrylate, decyl (meth)acrylate [decyl (meth)acrylate], tetradecyl (meth)acrylate [tetradecyl (meth)acrylate] ) acrylate], tridecyl acrylate, isodecyl (meth) acrylate, is
  • a heteroalicyclic (meth)acrylate monomer having 5 to 30 atoms phenyl epoxy acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxy cyclohexyl methyl (meth) acrylate, allyl glycidyl ether, etc.
  • epoxy mono(meth)acrylate aromatic mono(meth)acrylates such as phenol (EO) acrylate (PHEA), phenol (EO) 2 acrylate (PHEA-2), and phenol (EO) 4 acrylate (PHEA-4); caprolactone acrylate, 2-phenoxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, hydroxy Ethyl (meth)acrylamide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, methoxyethylene glycol modified (meth)acrylate, ethoxyethylene glycol modified (meth)acrylate, propoxyethylene glycol There are modified (meth)acrylate, methoxypropy
  • the monofunctional (meth)acrylate monomer may have a molecular weight of about 100 to 450 g/mol, and a glass transition temperature (Tg) in the range of about -80 to 150°C.
  • the monofunctional (meth) acrylate monomer is a first monofunctional (meth) acrylate monomer having a glass transition temperature of about -80 to -5 °C; and a second monofunctional (meth)acrylate monomer having a glass transition temperature of greater than about ⁇ 5° C. to about 150° C. or less.
  • the ratio (mixing ratio) of the first monofunctional (meth) acrylate monomer and the second monofunctional (meth) acrylate monomer may be 1: 0.3 to 6 by weight.
  • the monofunctional (meth) acrylate monomer is a first monofunctional (meth) acrylate monomer having a glass transition temperature of about -80 to -5 °C; and a second monofunctional (meth)acrylate monomer having a glass transition temperature of greater than about ⁇ 5° C. to about 150° C. or less; and an epoxy mono (meth) acrylate monomer.
  • the monofunctional (meth)acrylate monomer contains an epoxy mono(meth)acrylate monomer together with two types of monomers having different glass transition temperatures, high heat resistance and mechanical properties can be realized.
  • the ratio (mixing ratio) of the first monofunctional (meth) acrylate monomer and the second monofunctional (meth) acrylate monomer may be 1: 0.3 to 6 weight ratio, and the epoxy mono (meth)
  • the content of the acrylate monomer may be about 5 to 15% by weight based on the total amount of the monofunctional (meth)acrylate monomer.
  • the bifunctional (meth)acrylate monomer is a (meth)acrylate monomer containing two polymerizable functional groups (eg, (meth)acrylate groups) that are unsaturated groups capable of polymerization.
  • bifunctional (meth)acrylate monomer examples include: C 2 to C 30 alkylene glycol di(meth)acrylate monomer having an (meth)acrylate group and an alkylene structure in the molecule; There are ethoxylate di(meth)acrylate monomers having an ethylene oxide group in the molecule and having a (meth)acrylate group at the terminal by ethoxylation, but is not limited thereto. These may be used alone or two or more of them may be used in combination.
  • 1,6-hexanediol diacrylate (HDDA), 1,6-hexanediol dimethacrylate (HDDMA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), Polyethylene glycol 200 dimethacrylate (PEG200DMA), polyethylene glycol 300 diacrylate (PEG300DA), polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, diethylene glycol diacrylate Alkylene glycol di(s) such as derate (DEGDA), triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol diacrylate (TTEGDA), hydroxypivalate neopentyl glycol diacrylate (HPNDA), etc.
  • DEGDA derate
  • TEGDMA triethylene glycol dimethacrylate
  • TTEGDA tetraethylene glycol diacrylate
  • HPNDA hydroxypivalate neopentyl glycol
  • meth)acrylate monomers there are ethoxylated di(meth)acrylate monomers such as ethoxylated polypropylene glycol di(meth)acrylate and ethoxylated bisphenol A glycol dimethacrylate (Bis-EMA).
  • ethoxylated di(meth)acrylate monomers such as ethoxylated polypropylene glycol di(meth)acrylate and ethoxylated bisphenol A glycol dimethacrylate (Bis-EMA).
  • the bifunctional (meth)acrylate monomer is an alkylene glycol di(meth)acrylate monomer, more specifically 1,6-hexanediol diacrylate (HDDA), 1,6-hexanediol dimethacrylic rate (HDDMA), tripropylene glycol diacrylate (TPGDA), tripropylene glycol dimethacrylate, dipropylene glycol diacrylate (DPGDA), and dipropylene glycol dimethacrylate may be at least one selected from the group consisting of have.
  • HDDA 1,6-hexanediol diacrylate
  • HDDMA 1,6-hexanediol dimethacrylic rate
  • TPGDA tripropylene glycol diacrylate
  • DPGDA dipropylene glycol diacrylate
  • dipropylene glycol dimethacrylate dipropylene glycol dimethacrylate
  • the molecular weight of the bifunctional (meth)acrylate monomer is about 200 to 750 g/mol, and the glass transition temperature (Tg) may be in the range of about -45 to 110 °C.
  • the polyfunctional (meth)acrylate monomer has 3 or more (eg, 3 to 6, specifically 3 or 4) polymerizable functional groups that are unsaturated groups capable of polymerization (meth) It is an acrylate monomer.
  • a polyfunctional (meth)acrylate monomer can improve the adhesion of the coating film while improving the flowability, leveling property and workability of the composition.
  • the "polymerizable functional group” refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.
  • Non-limiting examples of such polyfunctional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, trimethylolpropane trifunctional (meth)acrylate monomers such as tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; tetrafunctional (meth) such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, etc.
  • acrylate monomers There are dipentaerythritol polyacrylate and the like, and these may be used alone or in combination of two or more.
  • the polyfunctional (meth)acrylate monomer may be trimethylolpropane tri(meth)acrylate.
  • the molecular weight of this trifunctional (meth)acrylate monomer is about 250 to 700 g/mol, and the glass transition temperature (Tg) may be in the range of about -10 to 280 °C.
  • the molecular weight of the tetrafunctional (meth)acrylate monomer is about 300 to 700 g/mol, and the glass transition temperature (Tg) may be in the range of about 0 to 300 °C.
  • the proportion of monofunctional (meth) Difunctional (meth) acrylate monomers and polyfunctional (meth) the total amount of acrylate monomer on the content of the acrylate monomer (W 1) (W 2 + W 3) [(W 2 +W 3 )/W 1 ] may range from about 0.1 to 0.25. If the weight ratio between the above-mentioned monomers is less than about 0.1, heat resistance and modulus are low, while when the weight ratio between the monomers is more than about 0.25, adhesive strength and rigid properties are low and small warpage Also, the reinforcing part may be peeled off from the flexible substrate or cracks may occur.
  • the content of the reactive monomer may be about 80 to 97 wt% based on the total weight of the oligomer and the reactive monomer, as described above.
  • the adhesion of the cured product may be improved by appropriately adjusting the curing density, and physical properties such as impact resistance and bendability may be improved.
  • the reactive monomer includes a monofunctional (meth) acrylate monomer, a bifunctional (meth) acrylate monomer, and a polyfunctional (meth) acrylate monomer, a monofunctional (meth) acrylate monomer, a bifunctional (
  • the ratio (mixing ratio) of the meth)acrylate monomer and the polyfunctional (meth)acrylate monomer may be 6-18: 1-5: 1 by weight.
  • the photopolymerization initiator is a component that is excited by ultraviolet rays or the like to initiate photopolymerization, and a conventional photopolymerization initiator in the art may be used without limitation.
  • Non-limiting examples of the photopolymerization initiator usable in the present invention include 2,4,6-trimethylbenzoyldiphenyl phosphine oxide (TPO), Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate (TPO-L), 2,2-Dimethoxy- 2-phenylacetophenone (DMPA), Irgacure 184, Irgacure 127, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Benzionalkylether, Benzophenone, Benzyl dimethyl BDK, Benzyl dimethyl BDK Cyclohexylphenylacetone (Hydroxycyclohexyl phenylacetone), chloroacetophenone (Chloroacetophenone), 1,1-dichloro acetophenone (1,1-Dichloro acetophenone), diethoxy acetophenone
  • the maximum absorption wavelength of the photopolymerization initiator is not particularly limited as long as it can absorb ultraviolet rays, and may be, for example, in the range of about 200 to 450 nm.
  • the content of the photopolymerization initiator may be about 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the oligomer and the photoreactive monomer.
  • the content of the photopolymerization initiator falls within the above-described range, hardness, adhesion, and the like of the cured product may be improved.
  • the curable composition of the present invention is an antistatic agent, hydrolysis inhibitor, silane-based compound, UV stabilizer, UV absorber, antioxidant, dispersant, antifoaming agent, as long as it does not affect the physical properties of the composition, in addition to the above-described oligomer, photoreactive monomer and photopolymerization initiator , a thickener, a plasticizer, a tackifying resin, and an additive such as a polymerization inhibitor may be further included.
  • the additive may include at least one selected from the group consisting of an antistatic agent, a hydrolysis inhibitor, and a silane-based compound.
  • additives may be used in a content range conventionally used in the art, for example, about 0.001 to 10 wt%, specifically about 0.01 to 5 wt%, more specifically about 0.1 to 5 wt%, based on the total amount of the composition can be
  • the antistatic agent usable in the present invention can be used without limitation as long as it is a material capable of preventing static electricity in the art.
  • metal cations eg, alkali metal cations, alkaline earth cations, specifically lithium (Li) cations
  • anions eg, bis(trifluoromethanesulfonyl)imide, tetrafluoroborate, hexafluorophosphate, bis(pentafluoroethanesulfonyl)imide, perfluorobutanesulfonate, heptafluorophosphate, (trifluoromethanesulfonyl)trifluoroacetamide, etc.].
  • examples of the antistatic agent include alkylammonium acetates, alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts, dodecyltrimethylammonium chloride, cetrimonium ammonium chloride, octadecyltrimethylammonium chloride, alkylpyridinium cationic surfactants such as salts, oxyalkylenealkylamines, and polyoxyalkylenealkylamines; Fatty acid soda soaps (eg sodium stearate soap, etc.), alkyl sulfates (eg sodium lauryl sulfate, etc.), alkyl ether sulfates, sodium alkylbenzenesulfonates, sodium alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkyl anionic surfactants such as phosphates and alkyldipheny
  • the content of the antistatic agent may be about 0.01 to 5 parts by weight, specifically about 0.1 to 5 parts by weight, based on 100 parts by weight, which is the total amount of the oligomer and the photoreactive monomer.
  • the hydrolysis inhibitor that can be used in the present invention is a component that imparts hydrolysis resistance of the cured product, and is not particularly limited as long as it is generally known in the art.
  • a carbodiimide-based compound for example, a carbodiimide-based compound, an epoxy compound, an isocyanate-based compound. compounds, oxazoline-based compounds, and the like.
  • the hydrolysis inhibitor may be a carbodiimide-based compound.
  • an aromatic carbodiimide-based compound is preferable in consideration of the hydrolysis resistance of the cured product and the dispersibility of the oligomer and the monomer in the composition.
  • aromatic carbodiimide compound examples include bis(2,6-dimethylphenyl)carbodiimide, bis(2,6-diisopropylphenyl)carboimide, bis(2,6-dit-butylphenyl)carboy bis(diC1-10 alkylphenyl)carboimide such as mide; diarylcarbodiimides such as diphenylcarbodiimide; bis(triC1-10 alkylphenyl)carboimide such as bis(2,4,6-triisopropylphenyl)carboimide, and the like, but is not limited thereto. These can be used individually or in combination of 2 or more types.
  • the content of the hydrolysis inhibitor may be about 0.01 to 5 parts by weight, specifically about 0.1 to 5 parts by weight, based on 100 parts by weight, which is the total amount of the oligomer and the photoreactive monomer.
  • silane-based compound (silane-based coupling agent) usable in the present invention is not particularly limited as long as it is known in the art, for example, 3-(glycidyloxy)propyltrimethoxysilane, 3-(glycidyloxy)propyltri Epoxy such as ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, epoxypropoxypropyl trimethoxysilane, etc.
  • silane coupling agents amino-based silane coupling agents such as 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; and a vinyl-based silane coupling agent such as 3-methacryloxypropyl trimethoxysilane.
  • the silane-based compound may be an epoxy-based silane coupling agent.
  • the content of the silane-based compound may be about 0.01 to 5 parts by weight, specifically about 0.1 to 5 parts by weight, based on 100 parts by weight, which is the total amount of the oligomer and the photoreactive monomer.
  • the curable composition according to the present invention may be applied to an organic light emitting display device through various coating methods known in the art.
  • coating methods usable in the present invention include inkjet printing, screen printing, transfer printing, spin coating, spray coating, dip coating, flow coating, doctor blade (doctor blade), dispensing (dispensing), flexographic printing (flexographic printing), gravure printing (gravure printing), offset printing (offset printing), gravure-offset printing, pad (pad) printing and the like.
  • the above-described curable composition is directly coated on the flexible substrate for a display panel, but in order to coat only the required region according to the bending region and the non-bending region of the flexible substrate, a non-contact direct coating method such as inkjet printing Through this, it is possible to directly form a layer (hereinafter, 'reinforcing part') capable of supporting and reinforcing the substrate on the flexible substrate.
  • inkjet printing can spray the curable composition at a desired position according to a computer-designed pattern, and at this time, since pressure is not applied to the flexible substrate, it is preferable to prevent damage to the flexible substrate.
  • FIG. 1 is a cross-sectional view schematically showing an organic light emitting display device according to the present invention
  • FIG. 2 is a plan view of the organic light emitting display device according to the present invention in a state in which the flexible substrate is not bent
  • FIG. It is a cross-sectional view showing an enlarged cross section of the square ( ⁇ ) part.
  • the organic light emitting diode display 10 of the present invention includes a flexible substrate 110 , a driving circuit unit 130 disposed on one surface of the flexible substrate 110 , and an organic light emitting device.
  • the reinforcing part 200 is formed by directly coating the above-described curable composition for inkjet, and has an adhesive force of about 150 gf/inch or more to the flexible substrate at about 25° C. measured according to ASTM D3330, and about 25° C.
  • the Young's modulus at is about 20 to 500 MPa.
  • the reinforcing part 200 has high modulus characteristics and excellent flexibility and adhesiveness, it is possible to stably support and reinforce the flexible substrate 110 of the display panel 100 . Accordingly, in the organic light emitting display device 10 of the present invention, the efficiency, productivity, and cost reduction effect of the module process during manufacturing may be improved, and durability and lifespan characteristics may be improved.
  • the display panel 100 is a portion that displays an image, and is an active area (A) in which pixels that actually emit light through the driving circuit unit 130 and the organic light emitting device 140 are disposed on the flexible substrate 110 . /A) and a non-active area (N/A) surrounding an edge of the display area A/A (refer to FIG. 2 ).
  • FIG. 2 is a plan view of a state in which the flexible substrate 110 of the organic light emitting diode display 10 according to the present invention is not bent.
  • the flexible substrate 110 supports and protects components of the organic light emitting display device 100 disposed thereon, and as shown in FIG. 1 , includes a first region P1; a bending region BP extending from one side of the first region P1; and a second region P2 extending from one side of the bending region B, wherein the second region P2 of the flexible substrate 110 faces at least a portion of the first region P1.
  • the first area P1 is disposed in the display area A/A including pixels that actually emit light through the organic light emitting device 140 , and the bending area BP and the second area P2 are It is disposed in the non-display area N/A.
  • the non-display area N/A of the flexible substrate 110 is a portion where wirings and driving circuits for driving a screen are disposed, and the wirings and driving circuits are formed on the substrate 110 as a gate in panel (GIP). It may be disposed or may be connected to the substrate 110 in a Tape Carrier Package (TCP) or Chip on Film (COF) method. Since the non-display area N/A of the flexible substrate 110 is not an area on which an image is displayed, it is not necessary to be visually recognized from the upper surface of the flexible substrate 110 . Accordingly, in the present invention, a portion of the non-display area N/A of the flexible substrate 110 is bent to secure an area for wiring and a driving circuit while reducing the bezel area.
  • GIP gate in panel
  • COF Chip on Film
  • a portion of the first region P1 and the second region P2 of the flexible substrate 110 are disposed to face each other, and at this time, the reinforcement disposed in each region P1 and P2
  • the parts 200 are attached to each other.
  • the wiring 120 formed in the non-display area N/A may transmit a signal by connecting a driving circuit, a gate driver, a data driver, or the like. Also, the wiring may be formed in the display area A/A.
  • the wiring may be formed of a conductive material such as gold (Au), silver (Ag), aluminum (Al), molybdenum (Mo), chromium (Cr), titanium (Ti), or nickel (Ni).
  • the flexible substrate 110 usable in the present invention is a plastic substrate in the form of a thin film made of a flexible material having flexible characteristics, and is not particularly limited as long as it is a curved surface and an insulating and heat-resistant polymer substrate.
  • Materials of such a flexible substrate include polyimide (PI), polyethersulfone (PES, polyethersulphone), polyacrylate (PAR, polyacrylate), polyetherimide (PEI, polyetherimide), and polyethylene naphthalate (PEN, polyethyelenen napthalate).
  • the flexible substrate 100 may be a polyimide substrate.
  • the polyimide since the polyimide has excellent mechanical strength and excellent heat resistance at a glass transition temperature of about 450° C., even if the manufacturing process of the display device is performed at a high temperature, it can stably serve as a substrate.
  • a buffer layer (not shown) may be further disposed on the flexible substrate 110 as described above.
  • the buffer layer may include at least one layer selected from among various inorganic layers and organic layers. Such a buffer layer may be omitted.
  • the driving circuit unit 130 is disposed on the flexible substrate 110 .
  • the driving circuit unit 130 includes a plurality of thin film transistors 131 and a power storage device (not shown), and drives the organic light emitting device 140 . That is, the organic light emitting device 140 displays an image by emitting light according to the driving signal received from the driving circuit unit 130 .
  • the thin film transistor 131 includes a gate electrode 132 , a source electrode 133 , a drain electrode 134 , and a semiconductor layer 135 , which are electrically connected to each other.
  • the gate electrode 132 , the source electrode 133 , and the drain electrode 134 are insulated by the interlayer insulating film 160
  • the gate insulating film 150 is between the gate electrode 132 and the semiconductor layer 135 .
  • insulated by The drain electrode 134 is electrically connected to the first electrode 141 of the organic light emitting device 140 through a contact hole provided in the planarization layer 170 .
  • the driving thin film transistor among the thin film transistors is illustrated in FIG. 3 .
  • a switching thin film transistor or the like may also be included in the display device.
  • the switching thin film transistor transfers the signal from the data line to the gate electrode of the driving thin film transistor.
  • the driving thin film transistor transmits a current transmitted through a power supply line to an anode according to a signal received from the switching thin film transistor, and light emission is controlled by the current transmitted to the anode.
  • the organic light emitting device 140 emits light according to a driving signal transmitted from the driving circuit unit 130 to display an image, and as shown in FIG. 3 , the flexible A first electrode 141 , a light emitting layer 142 , and a second electrode 143 are sequentially stacked on the substrate 110 .
  • the first electrode 141 is electrically connected to the drain electrode 134 of the thin film transistor 131 through a contact hole.
  • the first electrode 141 may be an anode
  • the second electrode 143 may be a cathode, and vice versa.
  • the light generated from the emission layer 142 passes through the second electrode 143 to emit light.
  • the organic light emitting diode display according to the present invention has a top emission type structure.
  • the anode is disposed on the substrate, and may be electrically connected to the driving thin film transistor to receive a driving current from the driving thin film transistor. Since the anode is formed of a material having a relatively high work function, holes are injected into an adjacent organic material layer, that is, a hole transport region (eg, a hole injection layer (not shown)).
  • a hole transport region eg, a hole injection layer (not shown)
  • the material for forming such a positive electrode is not particularly limited, and a conventional one known in the art may be used.
  • metals such as vanadium, chromium, copper, zinc, and gold
  • a cathode is disposed opposite to the anode, and specifically disposed on the electron transport region. Since the cathode is made of a material having a relatively low work function, electrons are injected into an adjacent organic material layer, that is, an electron transport region (eg, an electron injection layer (not shown)).
  • an electron transport region eg, an electron injection layer (not shown)
  • the material for forming the negative electrode is not particularly limited, and a conventional one known in the art may be used.
  • metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin, and lead; alloys thereof; and a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the light emitting layer 142 is a kind of organic material layer in which excitons are formed by combining holes and electrons respectively injected from the first electrode 141 and the second electrode 143 .
  • the emission color of the organic electroluminescent device may vary depending on the material constituting it.
  • the light emitting layer material is not particularly limited as long as it is a material for forming the light emitting layer known in the art.
  • the light emitting layer 142 is CBP (4,4'-bis(N-carbazolyl)-1,1'-biphenyl, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl) ), PVK (poly(n-vinylcabazole), poly(n-vinylcarbazole)), ADN (9,10-di(naphthalene-2-yl)anthracene, 9,10-di(naphthalen-2-yl)anthracene ) and the like host materials; and phosphorescent or fluorescent dopants such as organometallic complexes including Ir, Pt, Os, Re, Ti, Zr, Hf, or combinations of two or more thereof.
  • organometallic complexes including Ir, Pt, Os, Re, Ti, Zr, Hf, or combinations of two or more thereof.
  • a hole transport region specifically, at least one of a hole injection layer and a hole transport layer may be further disposed between the first electrode 141 and the emission layer 142 .
  • an electron transport region specifically, at least one of an electron transport layer and an electron injection layer may be further disposed between the emission layer 142 and the second electrode 143 .
  • Each of the hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer may be formed using a low molecular weight organic material or a high molecular weight organic material commonly known in the art.
  • a pixel defining layer 180 partitioning each pixel is disposed on the edges of the planarization layer 170 and the first electrode 141 .
  • the pixel defining layer 180 has an opening.
  • the opening of the pixel defining layer 180 exposes a portion of the first electrode 141 .
  • An emission layer 142 and a second electrode 143 are sequentially stacked on the first electrode 141 in the opening of the pixel defining layer 180 .
  • the second electrode 143 may be formed not only on the emission layer 142 but also on the pixel defining layer 180 .
  • the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may also be disposed between the pixel defining layer 180 and the second electrode 143 .
  • the organic light emitting device 140 emits light from the light emitting layer 142 positioned in the opening of the pixel defining layer 180 . Accordingly, the pixel defining layer 180 may define an emission region.
  • a capping layer may be disposed on the second electrode 143 .
  • the capping layer serves to protect the organic light emitting device 140 while helping the light generated from the light emitting layer to be efficiently emitted to the outside.
  • the capping layer may prevent loss of light from the second electrode through total reflection of light in the top emission type organic light emitting diode.
  • the capping layer is not particularly limited as long as it is a material that typically forms the capping layer in the art.
  • the display panel 100 of the present invention includes a thin film encapsulation layer 190 disposed on the second electrode 143 .
  • the thin film encapsulation layer 190 is a layer that protects the organic light emitting device 140 , and may have, for example, a structure in which inorganic layers 191 and 193 and organic layers 192 are alternately stacked. In FIG. 3 , the thin film encapsulation layer 190 includes two inorganic films 191 and 193 and one organic film 192 , but is not limited thereto. The thin film encapsulation layer 190 prevents external air, such as moisture or oxygen, from penetrating into the organic light emitting device 140 .
  • the inorganic layers 191 and 193 include an inorganic material selected from Al 2 O 3 , TiO 2 , ZrO, SiO 2 , AlON, AlN, SiON, Si 3 N4, ZnO, and Ta 2 O 5 .
  • the inorganic films 191 and 193 may be formed through a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method, but is not limited thereto, and the inorganic films 191 and 193 are not limited thereto. may be formed through various methods known to those skilled in the art. Such an inorganic film can suppress the penetration of moisture and oxygen.
  • the organic layer 192 is a thin film made of a polymer such as acrylic resin, epoxy resin, polyimide, and polyethylene, and may be formed through various methods known in the art, such as a thermal evaporation process.
  • the organic layer serves as a buffer layer for reducing stress between the inorganic layer 191 and the inorganic layer 193 , and allows the uppermost surface of the thin film encapsulation layer 190 to be flat.
  • the thin film encapsulation layer 190 may be used instead of the encapsulation substrate serving to encapsulate the organic light emitting device.
  • the organic light emitting display device may be a flexible display device.
  • an encapsulation substrate may be further disposed on the second electrode 143 .
  • the encapsulation substrate serves to encapsulate the organic light emitting device 140 together with the flexible substrate 110 .
  • the encapsulation substrate may be a plastic substrate.
  • the reinforcing part 200 is a part disposed on the other surface of the flexible substrate 110 of the above-described display panel 100 as shown in FIGS. 1 to 3 , and is flexible.
  • the substrate 110 may be supported and reinforced, and moisture or impurities may be prevented from penetrating from the outside.
  • the reinforcing part 200 is a surface opposite to the surface on which the organic light emitting diode 140 is disposed in the first area P1 and the second area P2 of the flexible substrate 110 except for the bending area BP. placed on top
  • the reinforcing part 200 may be disposed over the entire first area P1 , and may optionally be disposed over the entire second area P2 . That is, the reinforcing part 200 is formed by directly coating the inkjet curable composition on only a desired region according to the folded region and the non-folded region. Except for the bending region BP of the flexible substrate 110 , the remaining region of the first one side of the area P1; and one surface of the first area P1 among surfaces of the second area P2. Accordingly, when the flexible substrate 110 is bent, the reinforcing parts 200 respectively disposed in the first region P1 and/or the second region P2 are attached to face each other.
  • the reinforcing part 200 is a cured product of the aforementioned curable composition for inkjet, and has an adhesive force to the flexible substrate of about 150 gf/inch or more at about 25° C. measured according to ASTM D3330, and a Young’s modulus at about 25° C. about 20 to 500 MPa. As such, the reinforcing part 200 has a high modulus characteristic, and has excellent flexibility and adhesiveness. For this reason, the reinforcing part 200 offsets the stress generated in the area in contact with the flexible substrate 110 without separation (desorption) from the flexible substrate 110 when the flexible substrate 110 is bent, while the flexible substrate 110 is bent. ) can be stably supported and reinforced.
  • the organic light emitting diode display according to the present invention may have improved durability and lifespan characteristics.
  • the reinforcing part 200 is formed by directly coating the aforementioned curable composition for inkjet on a flexible substrate and selectively coating only a partial region, the organic light emitting diode display 10 of the present invention is manufactured The efficiency, productivity and cost savings of the city module process can be improved.
  • the reinforcing part 200 may have a Young's modulus of about 20 to 800 MPa measured at about 25°C after being left for about 24 hours under conditions of about 85°C and about 85%.
  • the reinforcing part 200 may satisfy Relation 1 below.
  • M 1 is the Young's modulus of the reinforcing part measured at about 25 °C
  • M 2 is the Young's modulus of the reinforcing part measured at about 25° C. after standing for about 24 hours under the conditions of about 85° C. and about 85%).
  • the organic light emitting display device of the present invention may have excellent high-temperature durability and lifespan characteristics.
  • the reinforcing part 200 may have a surface hardness in the range of about 2 to 20 MPa. As such, since the reinforcing part 200 has a high surface hardness, it is possible to protect the surface of the flexible substrate 110 from external impact.
  • the reinforcing part 200 has a 3 wt% loss temperature measured by thermogravimetric analysis (TGA) of about 180 ° C. or more, specifically, about 180 to 255 ° C., and has excellent heat resistance. For this reason, the organic light emitting display device of the present invention is excellent in high temperature reliability.
  • TGA thermogravimetric analysis
  • the thickness of the reinforcing part 200 is not particularly limited, and may be, for example, in the range of about 20 to 200 ⁇ m. However, it is preferable to adjust the thickness of the reinforcing part in consideration of the thickness of the flexible substrate 110 . According to an example, the ratio (T 2 /T 1 ) of the thickness of the reinforcing part (T 2 ) to the thickness (T 1 ) of the flexible substrate may be in the range of about 1 to 5.
  • the spacer 300 may be additionally further included between the reinforcing parts 200 respectively disposed in the first region P1 and the second region P2 opposite to each other. Such spacers 300 may be omitted.
  • the spacer 300 may fill a space between the reinforcing parts 200 respectively disposed in the first and second regions P1 and P2 facing each other to maintain a constant desired radius of curvature.
  • the radius of curvature of the bending region BP of the flexible substrate 110 may be easily adjusted by the spacer 300 .
  • the spacer 300 may be a foam tape made of various materials, but is not limited thereto.
  • the organic light emitting display device of the present invention may include a touch panel and/or a cover window respectively positioned on the display panel 100 .
  • the touch panel includes a touch sensor and is positioned on the display panel 100 through an optical adhesive layer.
  • the configuration and structure of the touch panel is not particularly limited, and may be a configuration and structure known in the art, and each configuration may be formed of a material known in the art.
  • cover window is attached to the touch panel through an optical adhesive to transmit light emitted from the display panel while protecting the display panel and the touch panel from external impact so that an image displayed on the display panel is visible from the outside.
  • a cover window may be made of a conventional material known in the art.
  • the organic light emitting display device of the present invention described above may be manufactured by various methods.
  • the reinforcing part 200 is formed on the surface opposite to the surface of the flexible substrate 110 on which the organic light emitting device is disposed through a direct coating method when manufacturing the organic light emitting display device.
  • the reinforcing part 200 may be selectively formed only in the remaining regions P1 and P2 except for the bending region BP of the flexible substrate 110 .
  • unlike the conventional lower reinforcement film made of an adhesive layer and a PET film there is no need to remove the portion of the reinforcement portion 200 corresponding to the bending region BP of the flexible substrate 110 .
  • the present invention can realize a large area of the organic light emitting display device because the reinforcing portion is formed by selectively coating the flexible substrate directly.
  • a method of manufacturing an organic light emitting display device includes forming a flexible substrate on a carrier substrate; forming a driving circuit unit and an organic light emitting device unit on one surface of the flexible substrate, respectively; forming a thin film encapsulation layer on the organic light emitting device unit; laminating a process protective film on the thin film encapsulation layer; separating the carrier substrate; and directly coating the aforementioned curable composition for inkjet on the other surface of the flexible substrate to form a reinforcing part.
  • the steps of each process may be modified or selectively mixed as needed.
  • a flexible substrate 110 is formed on a carrier substrate 1 .
  • a polyamic acid solution may be applied to one surface of the carrier substrate and dried to form the polyimide substrate 110 .
  • the carrier substrate 1 is not particularly limited as long as it is generally known in the art, and for example, a carrier glass substrate or the like.
  • the polyamic acid solution usable in the present invention is not particularly limited as long as it is generally known in the art.
  • the driving circuit unit 130 of the display panel 100 and the organic light emitting device 140 are respectively formed on one surface of the flexible substrate 110 , and then a thin film is encapsulated on the organic light emitting device 140 . A layer is formed (see FIGS. 5 and 6 ).
  • TFT thin film transistor
  • the interlayer insulating layer 160 is formed between the gate electrode 132 , the source electrode 133 , and the drain electrode 134
  • the gate insulating layer 150 is formed between the gate electrode 132 and the semiconductor layer 135 .
  • the drain electrode 134 is electrically connected to the first electrode 141 of the organic light emitting device 140 through a contact hole provided in the planarization layer 170 .
  • a planarization film 170 is formed on the entire surface of the flexible substrate 110 including the driving circuit unit 130 , and then a contact hole is formed in the planarization film 170 , and then the thin film transistor 131 )
  • a pixel defining layer 180 is formed on the planarization layer 170 .
  • the pixel defining layer 180 is formed to surround each pixel and overlap the edge of the first electrode 141 when viewed from the top, but is formed in a grid shape having a plurality of openings when viewed as a whole of the display panel.
  • a light emitting layer 142 is formed on the first electrode 141 .
  • the emission layer 142 may be formed on the pixel defining layer 180 as well as the first electrode 141 .
  • a hole injection layer and/or a hole transport layer may be positioned between the first electrode 141 and the emission layer 142 .
  • the second electrode 143 is formed on the entire surface of the substrate including the emission layer 142 .
  • the second electrode 143 may be formed only on the emission layer 142 .
  • the inorganic layers 191 and 193 and the organic layer 192 of the thin film encapsulation layer 190 may be sequentially formed on the second electrode 142 .
  • the organic light emitting device 140 in addition to the above-described driving circuit unit 130 , the organic light emitting device 140 , the planarization layer 170 , the pixel defining layer 180 , and the thin film encapsulation layer 190 , others generally known in the art
  • Other configurations of the display panel may be formed through methods known in the art.
  • a process film 2 may be attached on the display panel 100 .
  • the process film 2 is a film for protecting the upper part of the display panel, and is a peelable release protective film.
  • the process film 2 may be applied without limitation as long as it is a protective film for processes known in the art.
  • polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polychloride Vinyl film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone Films, polyetherimide films, polyimide films, fluororesin films, polyamide films, acrylic resin films, norbornene-based resin films, cycloolefin resin films, and the like.
  • PET polyethylene terephthalate
  • the curable composition for inkjet is directly coated on the flexible substrate 110 through a direct coating method such as inkjet printing, and the remaining region excluding the bending region BP of the flexible substrate 110, that is, the first region (
  • the reinforcing part 200 is formed by photocuring the curable composition by UV irradiation while selectively coating only P1) and the second region P2. Therefore, unlike the prior art, even without a partial cutting process of the film, as shown in FIG. 9( b ), the remaining areas other than the bending area BP of the flexible substrate 110 (that is, the first area P1 and the first area P1 ) The reinforcing part 200 may be easily formed only in the second region P2].
  • the ultraviolet irradiation may be performed at about 50 to 5,000 mJ for about 1 to 10 seconds.
  • the curing rate of the curable composition may be about 80% or more.
  • the flexible substrate 110 is bent so that the reinforcing parts 200 respectively disposed in the first region P1 and the second region P2 of the flexible substrate 110 face each other ( see Fig. 10).
  • a part of the reinforcement part 200 disposed on the first region P1 and the reinforcement part 200 disposed on the second region P2 are adhered to each other.
  • a spacer 300 may be additionally further disposed between the reinforcing parts 200 respectively disposed in the first region P1 and the second region P2 opposite to each other.
  • Curable compositions for inkjets of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared by mixing each component according to the composition shown in Table 1 below.
  • Table 1 the content unit of the oligomer and the reactive monomer is based on the total content of the oligomer and the reactive monomer in weight %, and the content unit of the photoinitiator and the auxiliary additive is in parts by weight, the total weight of the oligomer and the reactive monomer 100 weight based on wealth.
  • the specifications of the raw materials constituting each composition described in Table 1 are shown in Table 2 below.
  • Viscosity was measured using a Brookfield LVT model under the condition of #62 spindle, 200 rpm.
  • the surface tension was measured at 25°C using the DST-30 model of SEO company in the ring method method.
  • Example comparative example One 2 3 4 5 6 7 One 2 3 4 Viscosity (cPs) 27 25 26 26 28 26 24 43 29 49 27 Surface tension (dyne/cm) 32 30 32 35 33 34 32 37 41 43 36 Clogging (180 minutes) X X X X X X O X O Discharge straightness O O O O O O O X X O
  • Reinforcing parts in the display device were formed using the inkjet curable compositions of Examples 1 to 7 and Comparative Examples 1 to 4 as follows, and then the physical properties of the reinforcement parts were measured according to the following measurement methods, and the results are shown in the table below. 4 is shown. While directly printing each inkjet curable composition on the surface of a polyimide substrate (thickness: 20 ⁇ m), which is a flexible substrate of the flexible display panel, using an inkjet printer, LED UV lamps (wavelength: 365 nm) to form a reinforcing part (thickness: 50 ⁇ m) by photocuring under the conditions of 1,000 mW of light and 2 seconds. At this time, the reinforcing part was formed by selectively coating the curable composition on only the area other than the bending area on the surface of the polyimide substrate.
  • the composition After coating the composition on a flexible substrate (PI substrate), it is cured under the conditions of about 1,000 mW of light and 2 seconds in an LED UV lamp (wavelength: about 365 nm) in a nitrogen atmosphere, and then the adhesive strength between the cured product and the flexible substrate according to ASTM 3330 method was measured.
  • a composition cured under conditions of about 1,000 mW of light and 2 seconds in an LED UV lamp (wavelength: 365nm) in a nitrogen atmosphere was measured under ISO 14577-1 conditions using a nanoindenter manufactured by Micro Materials.
  • the 3 wt% loss temperature point of the reinforcing part was measured using the TGA 550 (TA instruments) equipment for the composition cured under the conditions of about 1,000 mW of light and 2 seconds in an LED UV lamp (wavelength: 365 nm) in a nitrogen atmosphere.
  • Example comparative example One 2 3 4 5 6 7 One 2 3 4 adhesion (gf/inch) 420 500 350 200 150 290 300 60 100 140 550 Young's modulus M 1 (MPa) 260 120 180 470 320 180 22 580 16 28 4 M 2 (MPa) 320 330 181 720 360 220 40 880 90 180 30 ⁇ M 0.81 0.36 0.99 0.76 0.89 0.82 0.55 0.66 0.18 0.16 0.13 Surface hardness (MPa) 7 10 9 17 20 5 4 22 3 5 2 TGA (3 wt% loss) (°C) 240 190 198 248 252 185 180 256 176 196 142

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Abstract

La présente invention concerne : une composition capable de former un film protecteur qui protège et sert de support à la partie inférieure d'un écran d'un dispositif d'affichage ; et un dispositif d'affichage comprenant ladite composition.
PCT/KR2020/018112 2019-12-16 2020-12-10 Composition durcissable pour impression à jet d'encre, et dispositif d'affichage électroluminescent organique la comprenant WO2021125695A1 (fr)

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KR10-2019-0167973 2019-12-16
KR1020190167973A KR20210076600A (ko) 2019-12-16 2019-12-16 잉크젯용 경화성 조성물 및 이를 포함하는 유기발광 표시장치

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KR102645392B1 (ko) * 2021-07-28 2024-03-11 한국다이요잉크 주식회사 전자기기의 제조를 위한 곡면 커버 부재의 제조방법
KR20230060582A (ko) 2021-10-27 2023-05-08 삼성디스플레이 주식회사 접착 부재 및 이를 포함하는 표시 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160046949A (ko) * 2014-10-20 2016-05-02 삼성에스디아이 주식회사 디스플레이 필름 및 이를 포함하는 디스플레이 장치
KR20180096448A (ko) * 2017-02-21 2018-08-29 삼성에스디아이 주식회사 윈도우 필름용 보호 필름, 이를 포함하는 광학 부재 및 이를 포함하는 디스플레이 장치
KR20180096997A (ko) * 2017-02-22 2018-08-30 동우 화인켐 주식회사 플렉시블 윈도우 적층체 및 이를 포함하는 화상 표시 장치
US20180371270A1 (en) * 2017-06-27 2018-12-27 Inx International Ink Co. Energy cured heat activated ink jet adhesives for foiling applications
KR20190110986A (ko) * 2015-08-31 2019-10-01 엘지디스플레이 주식회사 유기 발광 표시장치

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Publication number Priority date Publication date Assignee Title
KR20160046949A (ko) * 2014-10-20 2016-05-02 삼성에스디아이 주식회사 디스플레이 필름 및 이를 포함하는 디스플레이 장치
KR20190110986A (ko) * 2015-08-31 2019-10-01 엘지디스플레이 주식회사 유기 발광 표시장치
KR20180096448A (ko) * 2017-02-21 2018-08-29 삼성에스디아이 주식회사 윈도우 필름용 보호 필름, 이를 포함하는 광학 부재 및 이를 포함하는 디스플레이 장치
KR20180096997A (ko) * 2017-02-22 2018-08-30 동우 화인켐 주식회사 플렉시블 윈도우 적층체 및 이를 포함하는 화상 표시 장치
US20180371270A1 (en) * 2017-06-27 2018-12-27 Inx International Ink Co. Energy cured heat activated ink jet adhesives for foiling applications

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