WO2014109469A1 - Filler for organic light emitting diodes and organic light emitting device comprising same - Google Patents

Filler for organic light emitting diodes and organic light emitting device comprising same Download PDF

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Publication number
WO2014109469A1
WO2014109469A1 PCT/KR2013/010011 KR2013010011W WO2014109469A1 WO 2014109469 A1 WO2014109469 A1 WO 2014109469A1 KR 2013010011 W KR2013010011 W KR 2013010011W WO 2014109469 A1 WO2014109469 A1 WO 2014109469A1
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WIPO (PCT)
Prior art keywords
filler
light emitting
organic light
emitting device
meth
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PCT/KR2013/010011
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French (fr)
Korean (ko)
Inventor
황민규
김미선
백택진
서광원
송인재
이진아
최승집
Original Assignee
제일모직 주식회사
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Publication of WO2014109469A1 publication Critical patent/WO2014109469A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/02—Bonding areas; Manufacturing methods related thereto
    • H01L2224/04—Structure, shape, material or disposition of the bonding areas prior to the connecting process
    • H01L2224/05—Structure, shape, material or disposition of the bonding areas prior to the connecting process of an individual bonding area
    • H01L2224/05001—Internal layers
    • H01L2224/05099—Material
    • H01L2224/05198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/05298—Fillers
    • H01L2224/05299—Base material
    • H01L2224/0539—Base material with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/0635—Acrylic polymer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/874—Passivation; Containers; Encapsulations including getter material or desiccant

Definitions

  • the present invention relates to a filler for an organic light emitting device and an organic light emitting device including the same.
  • the organic light emitting device may be manufactured by disposing another substrate on a substrate on which an organic light emitting diode (organic light emitting diode, OLED) is deposited, and sealing both substrates.
  • OLED organic light emitting diode
  • the organic light emitting device is extremely weak in moisture, the interface between the metal electric field and the organic EL layer may be peeled off by water, and the organic material included in the organic electroluminescence (EL) may be altered by water.
  • the resistance can be increased by oxidizing the metal constituting the organic EL element.
  • the organic light emitting device includes a filler capable of filling the space between the substrate in addition to the sealing.
  • a small organic light emitting device for mobile uses a method of filling a space between a substrate on which a device is deposited and a substrate covering the substrate with a non-reactive inert gas as a filler.
  • a non-reactive inert gas as a filler.
  • filling with inert gas between substrates as in the past may cause bending due to the weight of the glass substrate.
  • the display unit is disposed inside the sealant, and is introduced into the core particles, the surface of the core particles and has at least one SiH group and at least one egg at the terminal.
  • a filler comprising a cured product of a polyorganosiloxane having a kenyl group is disclosed.
  • the remaining crosslinking agent including the crosslinking agent, may cause damage to the display unit.
  • An object of the present invention is to provide a filler for an organic light emitting device excellent in adhesion to the substrate can ensure a process and excellent reliability even under conditions of high temperature and high humidity after curing.
  • Another object of the present invention is to provide a filler for an organic light emitting device that can improve reliability by fast curing, and can suppress the occurrence and growth of dark spots by minimizing the content of residual monomers after curing.
  • Filler for an organic light emitting device may include a binder resin and an initiator having a curable functional group in the side chain.
  • Another organic light emitting device of the present invention may include a cured product of the filler for the organic light emitting device.
  • the present invention has a good adhesion to the substrate to ensure a process, and after curing provides a filler for organic light emitting device that is reliable even under conditions of high temperature and high humidity.
  • the present invention provides a filler for an organic light emitting device that can improve the reliability by fast curing, and can suppress the occurrence and growth of dark spots by minimizing the content of residual monomer even after curing.
  • FIG. 1 is a schematic cross-sectional view of an organic light emitting device of an embodiment of the present invention.
  • Filler for an organic light emitting device which is an aspect of the present invention may include a binder resin and an initiator having a curable functional group in the side chain.
  • the binder resin may have a curable functional group in the side chain of the binder resin.
  • a crosslinking density may be increased to provide a filler capable of securing reliability even at high temperature and high humidity.
  • the curing can be completed for a short time to improve the reliability by curing the binder resin.
  • the "side chain” is a branch portion connected to the main chain of the binder resin, and may preferably mean a branch portion except for the most end of the branch portions.
  • the "curable functional group” may be a thermosetting or photocurable functional group.
  • the curable functional group may be a (meth) acrylate group, a vinyl group, an epoxy group, or the like.
  • the curable functional group may be directly connected to the main chain of the binder resin by a side chain or to the side chain of the binder resin by a curable functional group providing compound.
  • the curable functional group providing compound may include a compound having a reactive functional group capable of bonding with the side chain of the binder resin and the curable functional group.
  • the curable functional group providing compound may include a compound having an isocyanate group and a (meth) acrylate group.
  • the curable functional group providing compound may be (meth) acryloyloxyalkyl isocyanate.
  • the curable functional group may be about 1% to about 10% by weight, preferably about 4% to about 9% by weight of the binder resin. In the above range, it is possible to secure the high temperature reliability after curing and to prevent defects due to curing shrinkage.
  • the weight average molecular weight of the binder resin may be about 300,000 g / mol to about 2,000,000 g / mol, preferably about 500,000 g / mol to about 1,000,000 g / mol. In the above range, it is included in the filler does not decompose even at high temperature conditions or the decomposition rate is low can provide high temperature reliability to the organic light emitting device, the mobility of the binder (mobility) is not high, so that the adhesiveness of the binder at room temperature and high temperature too high or The filler may not be so sticky that the adhesiveness may be increased without being too sticky.
  • the binder resin may have a glass transition temperature (Tg) of about + 10 ° C. or less, preferably about ⁇ 30 ° C. to about + 10 ° C. In the above range, it is possible to secure the flexibility to secure the adhesive force that can be attached to the organic light emitting device substrate to ensure flexibility, and may be attached to the organic light emitting device or the substrate.
  • Tg glass transition temperature
  • the binder resin may have a polydispersity of about 2.0 to about 3.0. In the above range, when the degree of dispersion of the binder is high, molecules having a low molecular weight may diffuse into the OLED device and may cause defects.
  • the binder resin may be included in about 90% to about 98% by weight of the filler, preferably about 96% to about 98% by weight. If additional photoinitiators and non-crosslinkable binders are present, residual photoinitiators and non-crosslinkable binders may diffuse over time and cause defects in the OLED device.In the case of hard materials such as inorganic fillers, OLED devices in the lamination process May cause a poor photographing.
  • the binder resin may include a polymer resin modified with a curable functional group.
  • the binder resin may be prepared by reacting a polymer resin having a hydroxyl group in a side chain, a reactive functional group capable of reacting with a hydroxyl group of the polymer resin, and a curable functional group providing compound having the curable functional group.
  • the reactive functional group may be an isocyanate group, but is not limited thereto. That is, by the hydroxyl group and the isocyanate group of the polymer resin, the binder resin may include a curable functional group in the side chain.
  • the binder resin may include Formula 1 in a side chain:
  • * is a linking site to the main chain of the binder resin
  • X is an acrylate group or methacrylate group
  • n and m are the same or different, and are an integer of 1 to 6).
  • (CH 2 ) n ” and “(CH 2 ) m ” may be linear or branched.
  • the polymer resin may include an acrylic binder.
  • acrylic may mean both acrylic and methacryl unless otherwise specified.
  • acrylic binder may mean both an acrylic binder after polymerization or pre-washing, or after purification or washing after polymerization.
  • the acrylic binder may have a polydispersity index (PDI) of about 3 or less, preferably about 2.0 to about 3.0. In the above range, the content of residual monomers and / or residual oligomers in the acrylic binder polymerization process is low, so that the amount of outgas generated is small, thereby providing reliability at high temperatures.
  • PDI polydispersity index
  • the acrylic binder may include an alkyl group, a hydroxyl group and a nitrile group.
  • the alkyl group may impart hydrophobicity when the acrylic binder is included as a filler to block contact with external moisture.
  • the nitrile group can increase the aggregation function between the binders and enhance the filling function.
  • the hydroxyl group can introduce a curable functional group into the side chain of the binder resin by reacting with the curable functional group providing compound.
  • the acrylic binder may be polymerized from a vinyl monomer having an alkyl group, a vinyl monomer having a nitrile group, a vinyl monomer having a hydroxyl group, or the monomer mixture. At least one of the vinyl monomers may be a (meth) acrylic monomer.
  • the vinyl monomer having an alkyl group may include a (meth) acrylic acid ester having a linear or branched alkyl group having 1 to 20 carbon atoms.
  • a (meth) acrylic acid ester having a linear or branched alkyl group having 1 to 20 carbon atoms.
  • the vinyl monomer having the nitrile group may be acrylonitrile, methacrylonitrile, or the like, but is not limited thereto.
  • the vinyl monomer having a hydroxyl group may include a (meth) acrylic acid ester having a hydroxyl group and an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms.
  • a (meth) acrylic acid ester having a hydroxyl group and an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms For example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1 , 6-hexanediol mono (meth)
  • the acrylic binder may include about 50% to about 80% by weight of a vinyl monomer having an alkyl group, about 10% to about 40% by weight of a vinyl monomer having a nitrile group, and about 1% to about 30% by weight of a vinyl monomer having a hydroxyl group. May contain%. In the above range, it is possible to form a binder as a filler, to improve flexibility, it may be possible to perform a lamination process without adding an additional inferior process to the glass.
  • about 60% to about 75% by weight of a vinyl monomer having an alkyl group, about 10% to about 20% by weight of a vinyl monomer having a nitrile group, and about 10% to about 20% by weight of a vinyl monomer having a hydroxyl group May contain%.
  • the acrylic binder may be polymerized by a suspension polymerization method.
  • the acrylic binder polymerized by suspension polymerization may have a low polydispersity and a low content of residual monomers and / or oligomers.
  • the acrylic binder polymerized by suspension polymerization may have a low polydispersity and a low content of residual monomers and / or oligomers.
  • it when included as a filler of the organic light emitting device, it does not decompose under high temperature conditions and does not generate outgas, thereby providing high temperature reliability for the organic light emitting device.
  • the PDI of the acrylic binder polymerized by the suspension polymerization method is about 1 to about 5, whereas the PDI of the acrylic binder polymerized by the solution polymerization method may be about 6 to about
  • the acrylic binder polymerized by the solution polymerization method has a higher polydispersity than the suspension polymerization method and has a high content of residual monomers or oligomers other than the polymer acrylic binder, and thus cannot provide high temperature reliability to the organic light emitting device when used as a filler. .
  • the acrylic binder may be polymerized by a conventional suspension polymerization method, preferably an aqueous solvent suspension polymerization.
  • the monomer mixture can be polymerized by vigorously stirring and dispersing the monomer mixture in an aqueous solvent and then adding a soluble initiator and heating.
  • the polymerization is not limited, but may be performed at a polymerization temperature of about 70 ° C to about 120 ° C for about 3 hours to about 12 hours.
  • the initiator is not limited to octane oil peroxide, decanyl oil peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, tert-butylperbenzo Ate, azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile and the like.
  • the content of the initiator and the method of dosing may be appropriately adjusted.
  • the initiator may be added in about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the monomer mixture.
  • the suspension polymerization may include a dispersant such as a water-soluble polymer to stabilize the dispersed monomer.
  • a dispersant such as a water-soluble polymer to stabilize the dispersed monomer.
  • acrylic acid, methacrylic acid alone or copolymers, or sodium salts, potassium salts or ammonium salts thereof can be further used. This is to stabilize the monomer further by maintaining proper solubility in the middle of the aqueous solvent which is a dispersion medium and the monomer suspended.
  • additives such as disodium hydrogen phosphate and sodium sulfate may be further included.
  • the additive may be included in about 0.01 parts by weight to about 5 parts by weight based on 100 parts by weight of the monomer mixture.
  • the curable functional group providing compound is a compound having an isocyanate group, and may be (meth) acryloyloxyalkyl (eg, an alkylene group having 1 to 10 carbon atoms) isocyanate or a mixture including the same, but is not limited thereto.
  • it may be (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, or the like.
  • the binder resin may be formed by polymerization of about 90% to about 99% by weight of the acrylic binder resin and about 1% to about 10% by weight of the curable functional group providing compound. In the above range, it is possible to secure the high temperature reliability after curing and to prevent defects due to curing shrinkage.
  • the acrylic binder resin may be formed by polymerization of about 91% to about 96% by weight and about 4% to about 9% by weight of the curable functional group providing compound.
  • the reaction between the acrylic binder resin and the curable functional group providing compound may be performed by a conventional method. In an embodiment, it can be carried out without a catalyst, but preferably in the presence of a catalyst for polymerization such as dibutyltindilaurate (DBTDL). In embodiments, the catalyst may be present in about 10ppm to about 300ppm with respect to the acrylic binder dissolution solution during the addition reaction.
  • a catalyst for polymerization such as dibutyltindilaurate (DBTDL).
  • DBTDL dibutyltindilaurate
  • the catalyst may be present in about 10ppm to about 300ppm with respect to the acrylic binder dissolution solution during the addition reaction.
  • the reaction may be performed at about 50 ° C. to about 55 ° C. for about 5 hours to about 10 hours, but is not limited thereto.
  • the binder resin may include an acrylic binder modified with (meth) acryloyloxyalkyl isocyanate.
  • the initiator may catalyze a curing reaction between the binder resins.
  • the initiator may comprise one or more of a thermosetting initiator and a photocuring initiator.
  • the initiator is a peroxide such as azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile, octane oil peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, and the like.
  • a peroxide such as azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile, octane oil peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, and the like.
  • Triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime or mixtures thereof but is not limited thereto.
  • the initiator may be included in about 2% to about 10% by weight, preferably about 2% to about 4% by weight of the filler. In the above range, it may cause a sufficient UV curing reaction, and if it contains an excessive amount of photoinitiator, it may cause a failure of the OLED device by the photoinitiator remaining after UV curing.
  • the filler may be formed of a filler composition including the binder resin and the initiator.
  • the composition may be prepared by coating on a release film and drying. The drying may be performed at about 80 ° C. to about 100 ° C. for about 5 minutes to about 15 minutes, but is not limited thereto.
  • the binder resin and the initiator in the composition are as described above. Based on the solids in the composition, the binder resin may be included in about 90% to about 98% by weight, the initiator may be included in about 2% to about 10% by weight.
  • the composition may further include a conventional solvent to increase the ease of coating of the composition.
  • the solvent may be methyl ethyl ketone or the like, but is not limited thereto.
  • the form of the filler is not limited, but may be in the form of a film.
  • the film may be an adhesive film having adhesion for adhesion of a substrate.
  • the adhesive film may have a thickness of about 5 ⁇ m to about 40 ⁇ m, preferably about 10 ⁇ m to about 20 ⁇ m. In the above range, it can be used as a filler in the organic light emitting device, there can be an effect that can be applied in various cases by varying the thickness of the film according to the gap (gap).
  • the filler may have a residual monomer content after curing of about 3000 ppm or less, preferably 0 ppm to about 500 ppm.
  • the residual monomer is a molecule having a weight average molecular weight of about 100 g / mol to about 1,000 g / mol, but may be unreacted monomers and oligomers in the manufacturing process of the binder resin, but is not limited thereto.
  • the filler may be used as a filler of an organic light emitting device by being a curable adhesive film and being filled between the substrate and the substrate including the organic light emitting device and cured.
  • An organic light emitting display device may include a cured product of the filler as a filler.
  • the organic light emitting device 100 includes a first substrate 110; A second substrate 120 disposed to face the first substrate 110; An organic light emitting diode (D) formed on the first substrate 110; A filler 170 may be included to cover the organic light emitting device D and fill a space between the first and second substrates 110 and 120.
  • the filler is in direct contact with part or all of the surface of the organic light emitting device to protect the organic light emitting device from the external environment, adhered to each of the first substrate and the second substrate, and connects the first substrate and the second substrate While filling the space formed between the first substrate and the second substrate.
  • the filler may include a cured product of the curable adhesive film.
  • the filler may be prepared by pressing the adhesive film on the organic light emitting device under vacuum and then curing.
  • the curing may include one or more of thermosetting and photocuring.
  • thermosetting may be performed at a temperature that does not affect the OLED device after panel fabrication
  • photocuring may be performed by applying a UV wavelength lamp that does not affect the OLED device after panel fabrication.
  • the filler may be used as a filler in a panel including a small organic as well as a large organic light emitting device.
  • a method of filling the space between the substrate and the substrate with an inert gas has been used.
  • the substrate may be bent due to the weight of the substrate, and the entire panel or the organic light emitting diode may be damaged by external impact. .
  • the filler even when the filler is applied to a large organic light emitting device, it protects the panel or the organic light emitting device from external impact and maintains stable light emission characteristics for a long time, thereby improving long-term reliability and suppressing the occurrence and growth of dark spots due to its good modulus and barrier properties. can do.
  • the first substrate may be a substrate having transparency.
  • the first substrate may be a flexible substrate or a non-flexible substrate.
  • the first substrate may be a glass substrate or a plastic substrate.
  • the material of the plastic substrate may be an insulating organic material, and for example, silicone resin, polyamide resin, epoxy resin, polyether sulfone resin, polyacrylate resin, polyetherimide resin, polyethylene naphthalate resin, polyethylene terephthalate resin , Polyphenylsulfide resin, polyarylate resin, polyimide resin, polycarbonate resin, cellulose resin and the like.
  • the organic light emitting diode may be formed on the first substrate.
  • 'upper' is referred to as 'upper' based on the drawings, and may be lower depending on the viewing point.
  • the organic light emitting diode may include an organic light emitting diode including an organic light emitting layer and the like and a plurality of thin film transistors connected to each organic light emitting layer.
  • the organic light emitting diode may be classified into a passive driving type and an active driving type according to whether the driving of the organic light emitting diode is controlled by the thin film transistor.
  • the organic light emitting device of the present invention can be applied to both passive driving type and active driving type.
  • the second substrate may face the first substrate and cover the organic light emitting diode in a contact or non-contact manner.
  • the second substrate may be formed of the same or different material as the first substrate.
  • the second substrate can be a glass substrate.
  • the organic light emitting device can be manufactured by a conventional method.
  • the composition for the adhesive film for the filler is coated on a release film and dried to prepare an adhesive film.
  • An adhesive film is laminated on a substrate in a single layer or a plurality of layers, and another substrate on which the organic light emitting element is formed is laminated so that the adhesive film and the organic light emitting element are in contact with each other.
  • an organic light emitting device filled with a filler may be manufactured by thermosetting or photocuring.
  • the organic light emitting device may further include a sealing material 150.
  • the sealing material is attached to only edge portions of the first substrate and the second substrate, respectively, without contacting the organic light emitting element, and seals a space between the first substrate and the second substrate, and prevents penetration of external moisture or oxygen.
  • the sealing material may be an organic material including an epoxy or the like, and an inorganic material such as a frit without using a separate absorbent may be used, but is not limited thereto.
  • the organic light emitting device includes a conventional element included in the conventional organic light emitting device, for example, a buffer layer for improving the smoothness of the first substrate and blocking the penetration of impurities, an organic film of the organic light emitting device, a sealing layer, and the like. It may further include.
  • BA butyl acrylate
  • EA ethyl acrylate
  • AN acrylonitrile
  • HEMA 2-hydroxyethyl methacrylate
  • An aqueous solution was prepared by dissolving 150 parts by weight of water and 0.1 parts by weight of polyvinyl alcohol in a stainless high pressure reactor equipped with a stirrer, adding 0.25 parts by weight of disodium hydrogen phosphate and 0.15 parts by weight of sodium sulfate.
  • the monomer mixture was added to the aqueous solution and stirred vigorously, and the inside of the reactor was filled with an inert gas such as nitrogen and argon and heated.
  • the reaction was terminated by suspension polymerization at 70 ° C for 1 hour and at 75 ° C for 5 hours.
  • an acrylic polyol binder was obtained through washing, dehydration, and drying, and then dissolved in methyl ethyl ketone (MEK) to prepare a solution of 15% solids.
  • MEK methyl ethyl ketone
  • a binder resin was prepared in the same manner as in Preparation Example 1, except that hexyl isocyanate was reacted without reacting the MOI.
  • Residual monomer content After curing 1.0g of the adhesive film under 350mJ / cm 2 condition, weigh the sample from 0.2g to 0.3g, add 9ml of analytical solvent such as chloroform (CHCl 3 ) and shaker for about 10 hours. To dissolve. Accurately measure 1 ml of internal standard solution, stir well, and filter with filter.
  • analytical solvent such as chloroform (CHCl 3 )
  • the filler for the organic light emitting device of the present invention can be easily adhered to the substrate with good adhesion.
  • the filler for the organic light emitting device of the present invention can be used as a reliable filler because no residual monomer is detected after curing and no dark spots occur.
  • the adhesive film of Comparative Example 1 containing an acrylic binder having no curable functional group in the side chain had good adhesiveness before crosslinking, but was unable to crosslink after curing, resulting in dark spots and poor reliability.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to a filler for organic light emitting diodes comprising a binder resin having a functional group with hardening properties at a side chain and an initiator, and an organic light emitting device including a hardening material thereof.

Description

유기발광소자용 충진제 및 이를 포함하는 유기발광장치Filler for organic light emitting device and organic light emitting device comprising the same
본 발명은 유기발광소자용 충진제 및 이를 포함하는 유기발광장치에 관한 것이다.The present invention relates to a filler for an organic light emitting device and an organic light emitting device including the same.
유기발광장치는 유기발광소자(유기발광다이오드, OLED)가 증착된 기판 위에 또 다른 기판을 배치하고, 상기 양 기판을 실링(sealing)하여 제조될 수 있다. 그러나, 유기발광소자는 수분에 극히 약하고, 금속 전계와 유기 EL 층과의 계면이 수분에 의해 박리되기도 하며, 유기 EL(electroluminescence)에 포함된 유기물이 수분에 의해 변질될 수도 있다. 또한, 유기 EL 소자를 구성하는 금속이 산화함으로써 저항이 높아질 수 있다. 이러한 이유로, 유기발광장치는 상기 실링 이외에도 기판과 기판 사이의 공간을 충진해 줄 수 있는 충진제를 포함한다.The organic light emitting device may be manufactured by disposing another substrate on a substrate on which an organic light emitting diode (organic light emitting diode, OLED) is deposited, and sealing both substrates. However, the organic light emitting device is extremely weak in moisture, the interface between the metal electric field and the organic EL layer may be peeled off by water, and the organic material included in the organic electroluminescence (EL) may be altered by water. In addition, the resistance can be increased by oxidizing the metal constituting the organic EL element. For this reason, the organic light emitting device includes a filler capable of filling the space between the substrate in addition to the sealing.
종래 모바일용인 소형의 유기발광장치는 소자가 증착된 기판과 그 위를 덮는 기판 사이의 공간을 반응성이 없는 inert gas를 충진제로 하여 충진하는 방식이 사용되었다. 그러나, TV 등의 대형 제품으로 개발이 확장되면서, 기존처럼 기판 사이를 inert gas로 충진하게 되면 유리 기판의 무게로 인한 휘어짐이 발생할 수 있다. 또한, 외부 충격에 의해 패널 전체 및 유기발광소자가 손상(damage)을 입을 수 있다는 문제점이 있다.Conventionally, a small organic light emitting device for mobile uses a method of filling a space between a substrate on which a device is deposited and a substrate covering the substrate with a non-reactive inert gas as a filler. However, as development expands to large products such as TVs, filling with inert gas between substrates as in the past may cause bending due to the weight of the glass substrate. In addition, there is a problem that the entire panel and the organic light emitting device may be damaged by an external impact.
이와 관련하여, 한국공개특허 제2011-0126378호에 따르면, 디스플레이부를 덮고 밀봉제 내측에 배치되며, 코어 입자, 상기 코어 입자의 표면에 도입되어 적어도 하나 이상의 SiH기를 갖는 가교제와 말단에 적어도 하나 이상의 알케닐기를 갖는 폴리오르가노실록산의 경화물을 포함하는 충진제를 개시하고 있다. 그러나, 가교제를 포함하여 잔류하는 가교제로 인해 디스플레이부에 손상을 일으킬 수 있다.In this regard, according to Korean Patent Laid-Open Publication No. 2011-0126378, the display unit is disposed inside the sealant, and is introduced into the core particles, the surface of the core particles and has at least one SiH group and at least one egg at the terminal. A filler comprising a cured product of a polyorganosiloxane having a kenyl group is disclosed. However, the remaining crosslinking agent, including the crosslinking agent, may cause damage to the display unit.
본 발명의 목적은 기판에 대한 점착성이 좋아 공정을 확보할 수 있고 경화 후에는 고온 및 고습의 조건에서도 신뢰성이 우수한 유기발광소자용 충진제를 제공하는 것이다.An object of the present invention is to provide a filler for an organic light emitting device excellent in adhesion to the substrate can ensure a process and excellent reliability even under conditions of high temperature and high humidity after curing.
본 발명의 다른 목적은 속 경화에 의해 신뢰성을 개선할 수 있고, 경화 후에도 잔류 모노머의 함량이 최소화됨으로써 다크 스폿의 발생 및 성장을 억제할 수 있는 유기발광소자용 충진제를 제공하는 것이다.Another object of the present invention is to provide a filler for an organic light emitting device that can improve reliability by fast curing, and can suppress the occurrence and growth of dark spots by minimizing the content of residual monomers after curing.
본 발명의 일 관점인 유기발광소자용 충진제는 측쇄에 경화성 작용기를 갖는 바인더 수지 및 개시제를 포함할 수 있다.Filler for an organic light emitting device that is an aspect of the present invention may include a binder resin and an initiator having a curable functional group in the side chain.
본 발명의 다른 관점인 유기발광장치는 상기 유기발광소자용 충진제의 경화물을 포함할 수 있다.Another organic light emitting device of the present invention may include a cured product of the filler for the organic light emitting device.
본 발명은 기판에 대한 점착성이 좋아 공정을 확보할 수 있고 경화 후에는 고온 고습의 조건에서도 신뢰성이 좋은 유기발광소자용 충진제를 제공하였다. 또한, 본 발명은 속 경화에 의해 신뢰성을 개선할 수 있고, 경화 후에도 잔류 모노머의 함량이 최소화됨으로써 다크 스폿의 발생 및 성장을 억제할 수 있는 유기발광소자용 충진제를 제공하였다.The present invention has a good adhesion to the substrate to ensure a process, and after curing provides a filler for organic light emitting device that is reliable even under conditions of high temperature and high humidity. In addition, the present invention provides a filler for an organic light emitting device that can improve the reliability by fast curing, and can suppress the occurrence and growth of dark spots by minimizing the content of residual monomer even after curing.
도 1은 본 발명 일 구체예의 유기발광장치의 개략적인 단면도이다.1 is a schematic cross-sectional view of an organic light emitting device of an embodiment of the present invention.
본 발명의 일 관점인 유기발광소자용 충진제는　측쇄에 경화성 작용기를 갖는 바인더 수지 및 개시제를 포함할 수 있다.Filler for an organic light emitting device which is an aspect of the present invention may include a binder resin and an initiator having a curable functional group in the side chain.
상기 바인더 수지는 바인더 수지의 측쇄에 경화성 작용기를 가질 수 있다. 상기 경화성 작용기로 인해 바인더 수지의 측쇄가 서로 가교되면서 가교 밀도를 높여 고온 및 고습에서도 신뢰성을 확보할 수 있는 충진제를 제공할 수 있다. 또한, 짧은 시간 동안 경화가 완료되어 바인더 수지를 경화시킴으로써 신뢰성을 개선할 수 있다.The binder resin may have a curable functional group in the side chain of the binder resin. As the side chains of the binder resin crosslink with each other due to the curable functional groups, a crosslinking density may be increased to provide a filler capable of securing reliability even at high temperature and high humidity. In addition, the curing can be completed for a short time to improve the reliability by curing the binder resin.
상기 “측쇄”는 상기 바인더 수지의 주쇄에 연결된 가지 부분으로서 바람직하게는 상기 가지 부분 중 최 말단을 제외한 가지 부분을 의미할 수 있다.The "side chain" is a branch portion connected to the main chain of the binder resin, and may preferably mean a branch portion except for the most end of the branch portions.
상기 “경화성 작용기”는 열경화 또는 광경화할 수 있는 작용기가 될 수 있다. 구체예에서, 상기 경화성 작용기는 (메타)아크릴레이트기, 비닐기, 에폭시기 등이 될 수 있다.The "curable functional group" may be a thermosetting or photocurable functional group. In an embodiment, the curable functional group may be a (meth) acrylate group, a vinyl group, an epoxy group, or the like.
상기 경화성 작용기는 측쇄로 상기 바인더 수지의 주쇄에 직접 연결되거나 경화성 작용기 제공 화합물에 의해 상기 바인더 수지의 측쇄에 연결될 수 있다. 상기 경화성 작용기 제공 화합물은 상기 바인더 수지의 측쇄와 결합할 수 있는 반응성 작용기 및 상기 경화성 작용기를 갖는 화합물을 포함할 수 있다. 구체예에서, 상기 경화성 작용기 제공 화합물은 이소시아네이트기와 (메타)아크릴레이트기를 갖는 화합물을 포함할 수 있다. 예를 들면, 상기 경화성 작용기 제공 화합물은 (메타)아크릴로일옥시알킬 이소시아네이트가 될 수 있다.The curable functional group may be directly connected to the main chain of the binder resin by a side chain or to the side chain of the binder resin by a curable functional group providing compound. The curable functional group providing compound may include a compound having a reactive functional group capable of bonding with the side chain of the binder resin and the curable functional group. In embodiments, the curable functional group providing compound may include a compound having an isocyanate group and a (meth) acrylate group. For example, the curable functional group providing compound may be (meth) acryloyloxyalkyl isocyanate.
상기 경화성 작용기는 상기 바인더 수지 중 약 1 중량% 내지 약 10 중량%, 바람직하게는 약 4 중량% 내지 약 9 중량%가 될 수 있다. 상기 범위에서, 경화후 고온 신뢰성 확보 및 경화 수축에 의한 불량을 예방할 수 있다. The curable functional group may be about 1% to about 10% by weight, preferably about 4% to about 9% by weight of the binder resin. In the above range, it is possible to secure the high temperature reliability after curing and to prevent defects due to curing shrinkage.
상기 바인더 수지의 중량평균분자량은 약 300,000 g/mol 내지 약 2,000,000 g/mol, 바람직하게는 약 500,000 g/mol내지 약 1,000,000 g/mol이 될 수 있다. 상기 범위에서, 충진제에 포함되어 고온 조건에서도 분해되지 않거나 분해 속도가 느려 유기발광소자에 고온 신뢰성을 제공할 수 있고, 바인더의 이동성(mobility)이 높지 않아 상온 및 고온에서 바인더의 점착성을 지나치게 높이거나 떨어뜨리지 않아 충진제가 너무 끈적이지 않으면서 밀착성은 높아지는 효과가 있을 수 있다.The weight average molecular weight of the binder resin may be about 300,000 g / mol to about 2,000,000 g / mol, preferably about 500,000 g / mol to about 1,000,000 g / mol. In the above range, it is included in the filler does not decompose even at high temperature conditions or the decomposition rate is low can provide high temperature reliability to the organic light emitting device, the mobility of the binder (mobility) is not high, so that the adhesiveness of the binder at room temperature and high temperature too high or The filler may not be so sticky that the adhesiveness may be increased without being too sticky.
상기 바인더 수지는 유리전이온도(Tg)가 약 +10℃ 이하, 바람직하게는 약 -30℃ 내지 약 +10℃가 될 수 있다. 상기 범위에서, 유연성을 확보하여 유기발광장치 기판에 점착할 수 있는 점착력을 확보하여 공정성을 확보할 수 있고, 유기발광소자 또는 기판에 부착 가능할 수 있다.The binder resin may have a glass transition temperature (Tg) of about + 10 ° C. or less, preferably about −30 ° C. to about + 10 ° C. In the above range, it is possible to secure the flexibility to secure the adhesive force that can be attached to the organic light emitting device substrate to ensure flexibility, and may be attached to the organic light emitting device or the substrate.
상기 바인더 수지는 다분산도가 약 2.0 내지 약 3.0이 될 수 있다. 상기 범위에서, 바인더의 분산도가 높아 낮은 분자량의 분자가 존재할 경우에는 OLED 소자에 확산되어 불량을 발생시킬 수 있다. The binder resin may have a polydispersity of about 2.0 to about 3.0. In the above range, when the degree of dispersion of the binder is high, molecules having a low molecular weight may diffuse into the OLED device and may cause defects.
상기 바인더 수지는 상기 충진제 중 약 90 중량% 내지 약 98 중량%, 바람직하게는 약 96 중량% 내지 약 98 중량%로 포함될 수 있다. 추가적인 광개시제 및 비가교성 바인더등이 존재할 경우 잔류하는 광개시제 및 비가교성 바인더의 경우 시간이 지나면서 확산되어 OLED 소자의 불량을 유발할 수 있으며, 무기 Filler등과 같이 딱딱한 물질의 경우 OLED 소자와 라미네이션 공정시 OLED 소자의 찍힘 불량을 유발할 수 있다.The binder resin may be included in about 90% to about 98% by weight of the filler, preferably about 96% to about 98% by weight. If additional photoinitiators and non-crosslinkable binders are present, residual photoinitiators and non-crosslinkable binders may diffuse over time and cause defects in the OLED device.In the case of hard materials such as inorganic fillers, OLED devices in the lamination process May cause a poor photographing.
상기 바인더 수지는 경화성 작용기로 변성된 고분자 수지를 포함할 수 있다. 구체예에서, 상기 바인더 수지는 측쇄에 수산기를 갖는 고분자 수지와, 상기 고분자 수지의 수산기와 반응할 수 있는 반응성 작용기 및 상기 경화성 작용기를 갖는 경화성 작용기 제공 화합물을 반응시킴으로써 제조될 수 있다. 예를 들면, 상기 반응성 작용기는 이소시아네이트기가 될 수 있지만, 이에 제한되지 않는다. 즉, 상기 고분자 수지의 수산기와 이소시아네이트기가 반응함으로써, 바인더 수지는 측쇄에 경화성 작용기를 포함할 수 있다.The binder resin may include a polymer resin modified with a curable functional group. In an embodiment, the binder resin may be prepared by reacting a polymer resin having a hydroxyl group in a side chain, a reactive functional group capable of reacting with a hydroxyl group of the polymer resin, and a curable functional group providing compound having the curable functional group. For example, the reactive functional group may be an isocyanate group, but is not limited thereto. That is, by the hydroxyl group and the isocyanate group of the polymer resin, the binder resin may include a curable functional group in the side chain.
구체예에서, 상기 바인더 수지는 측쇄에 하기 화학식 1을 포함할 수 있다:In an embodiment, the binder resin may include Formula 1 in a side chain:
<화학식 1><Formula 1>
* - (CH2)n - O - C(=O) - NH - 　(CH2)m - X*-(CH 2 ) n-O-C (= O)-NH-(CH 2 ) m-X
(상기에서, *는 바인더 수지의 주쇄에 대한 연결 부위이고, X는 아크릴레이트기 또는 메타크릴레이트기이고, n, m은 동일하거나 다르고, 1~6의 정수이다).(In the above, * is a linking site to the main chain of the binder resin, X is an acrylate group or methacrylate group, n and m are the same or different, and are an integer of 1 to 6).
상기에서 “(CH2)n”, “(CH2)m”은 선형 또는 분지형이 될 수 있다.In the above, “(CH 2 ) n ” and “(CH 2 ) m ” may be linear or branched.
일 실시예에서, 상기 고분자 수지는 아크릴계 바인더를 포함할 수 있다.In one embodiment, the polymer resin may include an acrylic binder.
본 명세서에서 “아크릴계”는 특별한 제한이 없는 한 아크릴계 및 메타아크릴계를 모두 의미할 수 있다.In the present specification, "acrylic" may mean both acrylic and methacryl unless otherwise specified.
본 명세서에서 “아크릴계 바인더”는 중합 후 정제 또는 수세 전 상태, 또는 중합 후 정제 또는 수세를 거친 상태의 아크릴계 바인더 모두를 의미할 수 있다.As used herein, the term "acrylic binder" may mean both an acrylic binder after polymerization or pre-washing, or after purification or washing after polymerization.
상기 아크릴계 바인더는 다분산지수(Polydispersity Index, PDI)가 약 3 이하, 바람직하게는 약 2.0 내지 약 3.0이 될 수 있다. 상기 범위에서, 아크릴계 바인더 중합 과정에서의 잔류 모노머 및/또는 잔류 올리고머의 함량이 낮아 아웃가스 발생량이 적어 고온에서　신뢰성을 제공할 수 있다. The acrylic binder may have a polydispersity index (PDI) of about 3 or less, preferably about 2.0 to about 3.0. In the above range, the content of residual monomers and / or residual oligomers in the acrylic binder polymerization process is low, so that the amount of outgas generated is small, thereby providing reliability at high temperatures.
상기 아크릴계 바인더는 알킬기, 수산기 및 니트릴기를 포함할 수 있다. 알킬기는 아크릴계 바인더를 충진제로 포함시 소수성을 부여하여 외부의 수분과의 접촉을 차단할 수 있다. 니트릴기는 바인더 간의 응집을 높여 충진 기능을 높일 수 있다. 수산기는 상기 경화성 작용기 제공 화합물과 반응함으로써 바인더 수지의 측쇄에 경화성 작용기를 도입할 수 있다.The acrylic binder may include an alkyl group, a hydroxyl group and a nitrile group. The alkyl group may impart hydrophobicity when the acrylic binder is included as a filler to block contact with external moisture. The nitrile group can increase the aggregation function between the binders and enhance the filling function. The hydroxyl group can introduce a curable functional group into the side chain of the binder resin by reacting with the curable functional group providing compound.
구체예에서, 상기 아크릴계 바인더는 알킬기를 갖는 비닐계 단량체, 니트릴기를 갖는 비닐계 단량체, 수산기를 갖는 비닐계 단량체, 또는 상기 단량체 혼합물로부터 중합될 수 있다. 상기 비닐계 단량체 중 하나 이상은 (메타)아크릴계 단량체가 될 수 있다.In an embodiment, the acrylic binder may be polymerized from a vinyl monomer having an alkyl group, a vinyl monomer having a nitrile group, a vinyl monomer having a hydroxyl group, or the monomer mixture. At least one of the vinyl monomers may be a (meth) acrylic monomer.
상기 알킬기를 갖는 비닐계 단량체는 탄소수 1~20의 선형 또는 분지형의 알킬기를 갖는 (메타)아크릴산 에스테르를 포함할 수 있다. 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, n-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, iso-부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 헥실 (메타)아크릴레이트, 헵틸 (메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 노닐 (메타)아크릴레이트, 데실 (메타)아크릴레이트 및 도데실 (메타)아크릴레이트로 이루어진 군으로부터 선택되는 1종 이상을 의미할 수 있지만, 이들에 제한되는 것은 아니다. The vinyl monomer having an alkyl group may include a (meth) acrylic acid ester having a linear or branched alkyl group having 1 to 20 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, iso-butyl (meth) acrylic Latex, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl ( It may mean one or more selected from the group consisting of metha) acrylate, decyl (meth) acrylate and dodecyl (meth) acrylate, but is not limited thereto.
상기 니트릴기를 갖는 비닐계 단량체는 아크릴로니트릴 및 메타크릴로니트릴 등이 될 수 있지만, 이에 제한되는 것은 아니다.The vinyl monomer having the nitrile group may be acrylonitrile, methacrylonitrile, or the like, but is not limited thereto.
상기 수산기를 갖는 비닐계 단량체는 수산기 및 탄소수 1~20의 알킬기 또는 탄소수 5~10의 사이클로알킬기를 갖는 (메타)아크릴산 에스테르를 포함할 수 있다. 예를 들면, 2-히드록시에틸 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 2-히드록시부틸 (메타)아크릴레이트, 6-히드록시헥실 (메타)아크릴레이트, 1,4-시클로헥산디메탄올 모노 (메타)아크릴레이트, 1-클로로-2-히드록시프로필 (메타)아크릴레이트, 디에틸렌글리콜 모노(메타)아크릴레이트, 1,6-헥산디올 모노(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 디펜타에리스리톨 펜타(메타)아크릴레이트, 네오펜틸글라이콜 모노(메타)아크릴레이트, 트리메틸올프로판 디(메타)아크릴레이트, 트리메틸올에탄 디(메타)아크릴레이트, 2-히드록시-3-페닐옥시프로필 (메타)아크릴레이트, 4-히드록시사이클로헥실 (메타)아크릴레이트, 2-히드록시-3-페닐옥시 (메타)아크릴레이트, 4-히드록시사이클로펜틸 (메타)아크릴레이트, 사이클로헥산디메탄올 모노(메타)아크릴레이트　중 하나 이상을 포함할 수 있다.The vinyl monomer having a hydroxyl group may include a (meth) acrylic acid ester having a hydroxyl group and an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. For example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1 , 6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) Acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy-3-phenyloxy (Meth) acrylate, 4-hydroxycyclophene (Meth) acrylate may include at least one of cyclohexane dimethanol mono (meth) acrylate.
상기 아크릴계 바인더는 알킬기를 갖는 비닐계 단량체 약 50 중량% 내지 약 80 중량%, 니트릴기를 갖는 비닐계 단량체 약 10 중량% 내지 약 40 중량%, 수산기를 갖는 비닐계 단량체 약 1 중량% 내지 약 30 중량%를 포함할 수 있다. 상기 범위에서, 충진제로서 바인더 형성이 가능하고, 유연성을 좋게 할 수 있으며, 글라스에 추가적인 열등의 공정을 가하지 않아도 라미네이션 공정이 가능할 수 있다. 바람직하게는, 알킬기를 갖는 비닐계 단량체 약 60 중량% 내지 약 75중량%, 니트릴기를 갖는 비닐계 단량체 약 10 중량% 내지 약 20 중량%, 수산기를 갖는 비닐계 단량체 약 10 중량% 내지 약 20 중량%를 포함할 수 있다.The acrylic binder may include about 50% to about 80% by weight of a vinyl monomer having an alkyl group, about 10% to about 40% by weight of a vinyl monomer having a nitrile group, and about 1% to about 30% by weight of a vinyl monomer having a hydroxyl group. May contain%. In the above range, it is possible to form a binder as a filler, to improve flexibility, it may be possible to perform a lamination process without adding an additional inferior process to the glass. Preferably, about 60% to about 75% by weight of a vinyl monomer having an alkyl group, about 10% to about 20% by weight of a vinyl monomer having a nitrile group, and about 10% to about 20% by weight of a vinyl monomer having a hydroxyl group May contain%.
상기 아크릴계 바인더는 현탁 중합법에 의해 중합될 수 있다. 현탁 중합에 의해 중합된 아크릴계 바인더는 다분산도가 낮으며, 잔류 모노머 및/또는 올리고머의 함량이 낮을 수 있다. 그 결과, 유기발광장치의 충진제로 포함시, 고온 조건에서도 분해되지 않고 아웃가스가 발생하지 않아 유기발광소자에 대해 고온 신뢰성을 제공할 수 있다. 또한, 유기발광장치의 충진제로 사용되었을 때 잔류 모노머 및/또는 잔류 올리고머 등의 저분자량 물질이 소자로 확산(diffusion)되어 이로부터 야기될 수 있는 결함, 예를 들면, 유기발광소자에 대한 손상(damage)을 최소화할 수 있다. 현탁 중합법으로 중합된 아크릴계 바인더의 PDI는 약 1 내지 약 5인데 비하여, 용액 중합법으로 중합된 아크릴계 바인더의 PDI는 약 6 내지 약 10이 될 수 있다.The acrylic binder may be polymerized by a suspension polymerization method. The acrylic binder polymerized by suspension polymerization may have a low polydispersity and a low content of residual monomers and / or oligomers. As a result, when included as a filler of the organic light emitting device, it does not decompose under high temperature conditions and does not generate outgas, thereby providing high temperature reliability for the organic light emitting device. In addition, when used as a filler of an organic light emitting device, defects that may occur due to diffusion of low molecular weight substances such as residual monomers and / or residual oligomers into the device, such as damage to the organic light emitting device ( damage can be minimized. The PDI of the acrylic binder polymerized by the suspension polymerization method is about 1 to about 5, whereas the PDI of the acrylic binder polymerized by the solution polymerization method may be about 6 to about 10.
반면에, 용액 중합법으로 중합된 아크릴계 바인더는 현탁 중합법에 비해 다분산도가 높으며, 고분자 아크릴계 바인더 이외의 잔류 모노머 또는 올리고머의 함량이　높아 충진제로서 사용시 유기발광장치에 고온 신뢰성을 제공할 수 없다.On the other hand, the acrylic binder polymerized by the solution polymerization method has a higher polydispersity than the suspension polymerization method and has a high content of residual monomers or oligomers other than the polymer acrylic binder, and thus cannot provide high temperature reliability to the organic light emitting device when used as a filler. .
일 실시예에서, 상기 아크릴계 바인더는 통상의 현탁 중합법, 바람직하게는 수계 용매 현탁 중합으로 중합될 수 있다.In one embodiment, the acrylic binder may be polymerized by a conventional suspension polymerization method, preferably an aqueous solvent suspension polymerization.
상기 현탁 중합에서는 단량체 혼합물을 수계 용매에서 강력하게 교반하여 분산시킨 후, 가용의 개시제를 첨가하고, 가열함으로써 중합할 수 있다. 상기 중합은 제한되지 않지만, 약 70℃ 내지 약 120℃의 중합 온도에서　약 3시간 내지 약 12시간 동안 수행될 수 있다.In the suspension polymerization, the monomer mixture can be polymerized by vigorously stirring and dispersing the monomer mixture in an aqueous solvent and then adding a soluble initiator and heating. The polymerization is not limited, but may be performed at a polymerization temperature of about 70 ° C to about 120 ° C for about 3 hours to about 12 hours.
상기 개시제로는 제한되지 않지만, 옥탄오일퍼옥사이드, 데칸오일퍼옥사이드, 라우로일퍼옥사이드, 벤조일퍼옥사이드, 모노클로로벤조일 퍼옥사이드, 디클로로벤조일퍼옥사이드, p-메틸벤조일퍼옥사이드, tert-부틸퍼벤조에이트, 아조비스이소부티로니트릴, 아조비스-(2,4-디메틸)발레로니트릴 등이 될 수 있다. 상기 개시제의 함량 및 투입 방법은 적절히 조절될 수 있다. 상기 개시제는 단량체 혼합물 100 중량부에 대해 약 0.01 중량부 내지 약 10 중량부로 투입될 수 있다.The initiator is not limited to octane oil peroxide, decanyl oil peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, tert-butylperbenzo Ate, azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile and the like. The content of the initiator and the method of dosing may be appropriately adjusted. The initiator may be added in about 0.01 parts by weight to about 10 parts by weight based on 100 parts by weight of the monomer mixture.
상기 현탁 중합에서는 분산된 단량체를 안정화시키기 위하여 수용성 고분자와 같은 분산제를 포함할 수 있다. 또한, 현탁 안정제로서 아크릴산, 메타크릴산 단독 또는 공중합체, 또는 이들의 나트륨염, 칼륨염, 또는 암모늄염을 더 사용할 수 있다. 이는 분산매인 수계 용매와 현탁되어 있는 단량체의 중간에서 적절한 용해도를 유지함으로써, 단량체를 보다 안정화시키기 위함이다.The suspension polymerization may include a dispersant such as a water-soluble polymer to stabilize the dispersed monomer. As the suspension stabilizer, acrylic acid, methacrylic acid alone or copolymers, or sodium salts, potassium salts or ammonium salts thereof can be further used. This is to stabilize the monomer further by maintaining proper solubility in the middle of the aqueous solvent which is a dispersion medium and the monomer suspended.
상기 현탁 중합에서는 디소듐 하이드로겐 포스페이트, 소듐 술페이트 등의 통상의 첨가제를 더 포함할 수 있다. 상기 첨가제는 단량체 혼합물 100 중량부에 대해 약 0.01 중량부 내지 약 5 중량부로 포함될 수 있다.In the suspension polymerization, conventional additives such as disodium hydrogen phosphate and sodium sulfate may be further included. The additive may be included in about 0.01 parts by weight to about 5 parts by weight based on 100 parts by weight of the monomer mixture.
상기 경화성 작용기 제공 화합물은 이소시아네이트기를 갖는 화합물로서, (메타)아크릴로일옥시알킬(예를 들면, 탄소수 1~10의 알킬렌기) 이소시아네이트 또는 이를 포함하는 혼합물이 될 수 있지만, 이에 제한되지 않는다. 예를 들면, (메타)아크릴로일옥시에틸 이소시아네이트 및 (메타)아크릴로일옥시프로필 이소시아네이트 등이 될 수 있다.The curable functional group providing compound is a compound having an isocyanate group, and may be (meth) acryloyloxyalkyl (eg, an alkylene group having 1 to 10 carbon atoms) isocyanate or a mixture including the same, but is not limited thereto. For example, it may be (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, or the like.
상기 바인더 수지는 상기 아크릴계 바인더 수지　약 90 중량% 내지 약 99 중량%, 상기 경화성 작용기 제공 화합물 약 1 중량% 내지 약 10 중량%의 중합으로 형성될 수 있다. 상기 범위에서, 경화후 고온 신뢰성 확보 및 경화 수축에 의한 불량을 예방할 수 있다.The binder resin may be formed by polymerization of about 90% to about 99% by weight of the acrylic binder resin and about 1% to about 10% by weight of the curable functional group providing compound. In the above range, it is possible to secure the high temperature reliability after curing and to prevent defects due to curing shrinkage.
　바람직하게는, 상기 아크릴계 바인더 수지 약 91 중량% 내지 약 96 중량%, 상기 경화성 작용기 제공 화합물 약 4 중량% 내지 약 9 중량%의 중합으로 형성될 수 있다.Preferably, the acrylic binder resin may be formed by polymerization of about 91% to about 96% by weight and about 4% to about 9% by weight of the curable functional group providing compound.
상기 아크릴계 바인더 수지와 경화성 작용기 제공 화합물 간의 반응은 통상의 방법으로 수행될 수 있다. 구체예에서, 촉매 없이 수행될 수 있지만, 바람직하게는 디부틸틴디라우레이트(DBTDL)와 같은 중합용 촉매 존재 하에서 수행될 수 있다. 구체예에서, 상기 촉매는 부가반응 진행시의 아크릴계 바인더 용해액에 대하여 약 10ppm 내지 약 300ppm으로 존재할 수 있다.The reaction between the acrylic binder resin and the curable functional group providing compound may be performed by a conventional method. In an embodiment, it can be carried out without a catalyst, but preferably in the presence of a catalyst for polymerization such as dibutyltindilaurate (DBTDL). In embodiments, the catalyst may be present in about 10ppm to about 300ppm with respect to the acrylic binder dissolution solution during the addition reaction.
상기 반응은 약 50℃ 내지 약 55℃에서 약 5 시간 내지 약 10시간 동안 수행될 수 있지만, 이에 제한되지 않는다.The reaction may be performed at about 50 ° C. to about 55 ° C. for about 5 hours to about 10 hours, but is not limited thereto.
바람직하게는, 상기 바인더 수지는 (메타)아크릴로일옥시알킬 이소시아네이트로 변성된 아크릴계 바인더를 포함할 수 있다.Preferably, the binder resin may include an acrylic binder modified with (meth) acryloyloxyalkyl isocyanate.
상기 개시제는 상기 바인더 수지 간의 경화 반응을 촉매할 수 있다. 구체예에서, 상기 개시제는 열경화 개시제 및 광경화 개시제 중 하나 이상을 포함할 수 있다.The initiator may catalyze a curing reaction between the binder resins. In embodiments, the initiator may comprise one or more of a thermosetting initiator and a photocuring initiator.
구체예에서, 상기 개시제는 아조비스이소부티로니트릴, 아조비스-(2,4-디메틸)발레로니트릴, 옥탄오일퍼옥사이드, 데칸오일퍼옥사이드, 라우로일퍼옥사이드, 벤조일퍼옥사이드 등의 퍼옥사이드, 트리아진계, 아세토페논계, 벤조페논계, 티오크산톤계, 벤조인계, 인계, 옥심계 또는 이들의 혼합물을 포함할 수 있지만, 이에 제한되지 않는다.In embodiments, the initiator is a peroxide such as azobisisobutyronitrile, azobis- (2,4-dimethyl) valeronitrile, octane oil peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, and the like. , Triazine, acetophenone, benzophenone, thioxanthone, benzoin, phosphorus, oxime or mixtures thereof, but is not limited thereto.
상기 개시제는 상기 충진제 중 약 2 중량% 내지 약 10 중량%, 바람직하게는 약 2 중량% 내지 약 4 중량%로 포함될 수 있다. 상기 범위에서,　충분한 UV경화 반응을 일으킬수 있으며, 과량의 광개시제 포함할 경우, UV 경화 후 잔류하는 광개시제에 의하여 OLED 소자의 불량을 유발할 수 있다.The initiator may be included in about 2% to about 10% by weight, preferably about 2% to about 4% by weight of the filler. In the above range, it may cause a sufficient UV curing reaction, and if it contains an excessive amount of photoinitiator, it may cause a failure of the OLED device by the photoinitiator remaining after UV curing.
상기 충진제는 상기 바인더 수지 및 개시제를 포함하는 충진제용 조성물로 형성될 수 있다. 구체예에서, 상기 조성물을 이형 필름 위에 코팅하고, 건조시킴으로써 제조될 수 있다. 상기 건조는 약 80℃ 내지 약 100℃에서 약 5분 내지 약 15분　수행될 수 있는데, 이에 제한되지 않는다.The filler may be formed of a filler composition including the binder resin and the initiator. In an embodiment, the composition may be prepared by coating on a release film and drying. The drying may be performed at about 80 ° C. to about 100 ° C. for about 5 minutes to about 15 minutes, but is not limited thereto.
상기 조성물 중 상기 바인더 수지 및 개시제에 대한 내용은 상술한 바와 같다. 상기 조성물 중 고형분 기준으로, 상기 바인더 수지는 약 90 중량% 내지 약 98중량%, 상기 개시제는 약 2 중량% 내지 약 10 중량%로 포함될 수 있다.Details of the binder resin and the initiator in the composition are as described above. Based on the solids in the composition, the binder resin may be included in about 90% to about 98% by weight, the initiator may be included in about 2% to about 10% by weight.
상기 조성물은 조성물의 코팅 용이성을 높이기 위하여 통상의 용제를 더 포함할 수 있다. 구체예에서, 상기 용제는 메틸에틸케톤 등이 될 수 있지만, 이에 제한되지는 않는다.The composition may further include a conventional solvent to increase the ease of coating of the composition. In embodiments, the solvent may be methyl ethyl ketone or the like, but is not limited thereto.
상기 충진제의 형태는 제한되지 않지만, 필름 형태가 될 수 있다. 상기 필름은 기판의 접착을 위해 접착성을 갖는 접착 필름이 될 수 있다.The form of the filler is not limited, but may be in the form of a film. The film may be an adhesive film having adhesion for adhesion of a substrate.
상기 접착 필름의 두께는 약 5㎛ 내지 약 40㎛, 바람직하게는 약 10㎛ 내지 약 20㎛가 될 수 있다. 상기 범위에서, 유기발광장치에 충진제로 사용될 수 있고, 갭(gap)에 따라 필름의 두께를 다양하게 조절하여 여러 경우에 적용할 수 있는 효과가 있을 수 있다.The adhesive film may have a thickness of about 5 μm to about 40 μm, preferably about 10 μm to about 20 μm. In the above range, it can be used as a filler in the organic light emitting device, there can be an effect that can be applied in various cases by varying the thickness of the film according to the gap (gap).
상기 충진제는 경화 후 잔류 모노머 함량이 약 3,000ppm 이하, 바람직하게는 0 ppm 내지 약 500 ppm이 될 수 있다. 상기 잔류 모노머는 중량평균분자량이 약 100 g/mol 내지 약 1,000 g/mol인 분자로서, 상기 바인더 수지의 제조 과정에서 미반응 모노머　및 올리고머　등이 될 수 있지만, 이에 제한되지 않는다. The filler may have a residual monomer content after curing of about 3000 ppm or less, preferably 0 ppm to about 500 ppm. The residual monomer is a molecule having a weight average molecular weight of about 100 g / mol to about 1,000 g / mol, but may be unreacted monomers and oligomers in the manufacturing process of the binder resin, but is not limited thereto.
상기 충진제는 경화성 접착 필름으로, 유기발광소자를 포함하는 기판과 기판 사이에 충진된 후 경화됨으로써 유기발광장치의 충진제로 사용될 수 있다.The filler may be used as a filler of an organic light emitting device by being a curable adhesive film and being filled between the substrate and the substrate including the organic light emitting device and cured.
본 발명의 다른 관점인 유기발광표시장치는 상기 충진제의 경화물을 충진제로 포함할 수 있다.An organic light emitting display device according to another aspect of the present invention may include a cured product of the filler as a filler.
도 1은 본 발명 일 구체예의 유기발광장치를 개략적으로 도시한 단면도이다. 도 1에서 도시된 바와 같이, 유기발광장치(100)는 제1 기판(110); 상기 제1 기판(110)과 대향하도록 배치된 제2 기판(120); 상기 제1 기판(110) 상부에 형성된 유기발광소자(D); 상기 유기발광소자(D)를 덮고 상기 제1 기판(110)과 제2 기판(120) 사이의 공간을 충진하는 충진제(170)를 포함할 수 있다.1 is a cross-sectional view schematically showing an organic light emitting device according to an embodiment of the present invention. As shown in FIG. 1, the organic light emitting device 100 includes a first substrate 110; A second substrate 120 disposed to face the first substrate 110; An organic light emitting diode (D) formed on the first substrate 110; A filler 170 may be included to cover the organic light emitting device D and fill a space between the first and second substrates 110 and 120.
상기 충진제는 유기발광소자의 표면의 일부 또는 전부와 직접적으로 접촉하여 외부 환경으로부터 유기발광소자를 보호하고, 상기 제1 기판과 제2 기판 각각에 접착되고, 상기 제1 기판과 제2 기판을 연결하면서 상기 제1 기판과 제2 기판 사이에 형성된 공간을 충진하는 역할을 한다.The filler is in direct contact with part or all of the surface of the organic light emitting device to protect the organic light emitting device from the external environment, adhered to each of the first substrate and the second substrate, and connects the first substrate and the second substrate While filling the space formed between the first substrate and the second substrate.
상기 충진제는 상기 경화성 접착 필름의 경화물을 포함할 수 있다. 구체예에서, 상기 충진제는 진공 하에서 상기 유기발광소자에 상기 접착 필름을 압착한 후 경화시켜 제조될 수 있다. 예를 들면, 상기 경화는 열경화, 광경화 중 하나 이상을 포함할 수 있다. 구체예에서, 열경화는 패널 제작후 OLED 소자에 영향을 주지 않는 온도에서 수행될 수 있고, 광경화는 패널 제작후 OLED 소자에 영향을 미치지 않는 UV 파장 Lamp를 적용하여 진행할 수 있다.The filler may include a cured product of the curable adhesive film. In embodiments, the filler may be prepared by pressing the adhesive film on the organic light emitting device under vacuum and then curing. For example, the curing may include one or more of thermosetting and photocuring. In an embodiment, thermosetting may be performed at a temperature that does not affect the OLED device after panel fabrication, and photocuring may be performed by applying a UV wavelength lamp that does not affect the OLED device after panel fabrication.
상기 충진제는 소형뿐만 아니라 대형 유기발광소자를 포함하는 패널에서 충진제로 사용할 수 있다. 기존의 소형의 유기발광장치에서는 기판과 기판 사이의 공간을 불활성가스(inert gas)로 충진하는 방식이 사용되었다. 그러나, TV 등 대형 제품으로 개발이 확장되면 기판 사이를 상기 inert gas로 충진할 경우 기판의 무게로 인해 기판의 휘어짐이 발생할 수 있고, 외부 충격에 의해 패널 전체 또는 유기발광소자가 손상을 입을 수 있다. The filler may be used as a filler in a panel including a small organic as well as a large organic light emitting device. In the existing small organic light emitting device, a method of filling the space between the substrate and the substrate with an inert gas has been used. However, if the development is extended to a large product such as a TV, when the inert gas is filled between the substrates, the substrate may be bent due to the weight of the substrate, and the entire panel or the organic light emitting diode may be damaged by external impact. .
반면에 상기 충진제는 대형의 유기발광장치에 적용되더라도 외부 충격으로부터 패널 또는 유기발광소자를 보호하여 장기간 안정한 발광 특성을 유지함으로써 장기 신뢰성을 높이고, 모듈러스 및 배리어 특성이 좋아 다크 스폿의 발생 및 성장을 억제할 수 있다.On the other hand, even when the filler is applied to a large organic light emitting device, it protects the panel or the organic light emitting device from external impact and maintains stable light emission characteristics for a long time, thereby improving long-term reliability and suppressing the occurrence and growth of dark spots due to its good modulus and barrier properties. can do.
상기 제1 기판은 투명성이 있는 기판이 될 수 있다. 구체예에서, 상기 제1기판은 플렉시블(flexible) 기판 또는 비 플렉시블(non-flexible) 기판이 될 수 있다. 예를 들면, 상기 제1 기판은 유리 기판 또는 플라스틱 기판이 될 수 있다. 상기 플라스틱 기판의 재료는 절연성 유기물일 수 있고, 예를 들면, 실리콘계 수지, 폴리아미드 수지, 에폭시 수지, 폴리에테르술폰 수지, 폴리아크릴레이트 수지, 폴리에테르이미드 수지, 폴리에틸렌나프탈레이트 수지, 폴리에틸렌테레프탈레이트 수지, 폴리페닐술파이드 수지, 폴리아릴레이트 수지, 폴리이미드 수지, 폴리카보네이트 수지 및 셀룰로오스계 수지 등이 될 수 있다.The first substrate may be a substrate having transparency. In embodiments, the first substrate may be a flexible substrate or a non-flexible substrate. For example, the first substrate may be a glass substrate or a plastic substrate. The material of the plastic substrate may be an insulating organic material, and for example, silicone resin, polyamide resin, epoxy resin, polyether sulfone resin, polyacrylate resin, polyetherimide resin, polyethylene naphthalate resin, polyethylene terephthalate resin , Polyphenylsulfide resin, polyarylate resin, polyimide resin, polycarbonate resin, cellulose resin and the like.
상기 유기발광소자는 상기 제1 기판 상부에 형성되어 있을 수 있다.The organic light emitting diode may be formed on the first substrate.
본 명세서에서 ‘상부’는 도면을 기준으로 ‘상부’로 칭한 것으로서, 보는 시각에 따라서는 하부가 될 수 있다.In the present specification, 'upper' is referred to as 'upper' based on the drawings, and may be lower depending on the viewing point.
상기 유기발광소자는 유기발광층 등을 포함하는 유기발광소자 및 각 유기발광층에 접속된 박막 트랜지스터 복수 개를 포함할 수 있다. 각 유기발광소자의 구동을 박막 트랜지스터로 제어하는지 여부에 따라 수동 구동형과 능동 구동형으로 구분될 수 있다. 본 발명의 유기발광장치는 수동 구동형과 능동 구동형 모두에 적용될 수 있다.The organic light emitting diode may include an organic light emitting diode including an organic light emitting layer and the like and a plurality of thin film transistors connected to each organic light emitting layer. The organic light emitting diode may be classified into a passive driving type and an active driving type according to whether the driving of the organic light emitting diode is controlled by the thin film transistor. The organic light emitting device of the present invention can be applied to both passive driving type and active driving type.
상기 제2 기판은 상기 제1 기판과 대향하고 상기 유기발광소자를 접촉 또는 비접촉 방식으로 덮을 수 있다. 상기 제2 기판은 상기 제1 기판과 동일하거나 또는 다른 소재로 형성될 수 있다. 구체예에서, 상기 제2 기판은 유리 기판이 될 수 있다.The second substrate may face the first substrate and cover the organic light emitting diode in a contact or non-contact manner. The second substrate may be formed of the same or different material as the first substrate. In an embodiment, the second substrate can be a glass substrate.
상기 유기발광장치는 통상의 방법으로 제조될 수 있다. 예를 들면, 상기 충진제용 접착 필름용 조성물을 이형 필름 위에 코팅하고 건조시켜 접착 필름을 제조한다. 기판 위에 접착 필름을 단일층 또는 복수층으로 적층하고, 유기발광소자가 형성된 또 다른 기판을 상기 접착 필름과 유기발광소자가 접촉하도록 합지한다. 그런 다음, 열경화 또는 광경화시킴으로써 충진제로 충진된 유기발광장치를 제조할 수 있다.The organic light emitting device can be manufactured by a conventional method. For example, the composition for the adhesive film for the filler is coated on a release film and dried to prepare an adhesive film. An adhesive film is laminated on a substrate in a single layer or a plurality of layers, and another substrate on which the organic light emitting element is formed is laminated so that the adhesive film and the organic light emitting element are in contact with each other. Then, an organic light emitting device filled with a filler may be manufactured by thermosetting or photocuring.
상기 유기발광장치는 실링재(150)를 더 포함할 수 있다. The organic light emitting device may further include a sealing material 150.
상기 실링재는 유기발광소자에 접촉 없이 상기 제 1기판과 제2 기판의 가장자리 부분에만 각각 부착되어, 상기 제1 기판과 제2 기판 사이의 공간을 밀봉하고, 외부의 수분 또는 산소의 투과를 방지할 수 있다. 상기 실링재는 에폭시 등을 포함하는 유기재, 별도의 흡습제를 사용할 필요가 없는 프릿(frit)과 같은 무기재를 사용할 수 있지만, 이에 제한되지 않는다.The sealing material is attached to only edge portions of the first substrate and the second substrate, respectively, without contacting the organic light emitting element, and seals a space between the first substrate and the second substrate, and prevents penetration of external moisture or oxygen. Can be. The sealing material may be an organic material including an epoxy or the like, and an inorganic material such as a frit without using a separate absorbent may be used, but is not limited thereto.
상기 유기발광장치는 통상의 유기발광장치에 포함되는 통상의 요소, 예를 들면 상기 제1 기판의 평활성을 개선하고 불순 원소의 침투를 차단하기 위한 버퍼층, 유기발광소자의 유기막, 밀봉층 등을 더 포함할 수 있다.The organic light emitting device includes a conventional element included in the conventional organic light emitting device, for example, a buffer layer for improving the smoothness of the first substrate and blocking the penetration of impurities, an organic film of the organic light emitting device, a sealing layer, and the like. It may further include.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.
제조예 1 내지 3: 바인더 수지의 제조Preparation Examples 1 to 3: Preparation of Binder Resin
부틸 아크릴레이트(BA), 에틸 아크릴레이트(EA), 아크릴로나이트릴(AN), 2-하이드록시에틸메타아크릴레이트(HEMA)를 이용하여 하기 표 1(단위: 중량부)의 조성표와 같이 단량체 혼합액에 아조비스이소부티로니트릴 0.3 중량부를 혼합하여 완전히 균일하게 만들었다. 교반기가 부착된 스테인레스 고압 반응기에 물 150 중량부 및 폴리비닐알코올 0.1 중량부를 용해시키고, 디소듐 하이드로겐 포스페이트 0.25 중량부, 소듐 술페이트 0.15 중량부를 첨가하여 수용액을 제조하였다. 상기 수용액에 단량체 혼합액을 투입하고 강하게 교반하며, 질소, 아르곤 등의 불활성 기체로 반응기 내부를 채우고 가열하였다. 70℃에서 1시간, 75℃에서 5 시간을 현탁 중합하여 반응을 종결하였다. 반응이 종결된 후 세척, 탈수, 건조를 통해 아크릴계 폴리올 바인더를 얻은 후 메틸에틸케톤(MEK)에 용해하여 고형분 15%의 용액을 제조하였다.Using butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), 2-hydroxyethyl methacrylate (HEMA) as shown in the composition table of Table 1 (unit: parts by weight) 0.3 parts by weight of azobisisobutyronitrile was mixed with the mixed solution to make it completely uniform. An aqueous solution was prepared by dissolving 150 parts by weight of water and 0.1 parts by weight of polyvinyl alcohol in a stainless high pressure reactor equipped with a stirrer, adding 0.25 parts by weight of disodium hydrogen phosphate and 0.15 parts by weight of sodium sulfate. The monomer mixture was added to the aqueous solution and stirred vigorously, and the inside of the reactor was filled with an inert gas such as nitrogen and argon and heated. The reaction was terminated by suspension polymerization at 70 ° C for 1 hour and at 75 ° C for 5 hours. After the reaction was completed, an acrylic polyol binder was obtained through washing, dehydration, and drying, and then dissolved in methyl ethyl ketone (MEK) to prepare a solution of 15% solids.
상기 제조한 아크릴계 폴리올 바인더에 메타아크릴로일옥시에틸 이소시아네이트(methacryloyloxyethyl isocyanate, MOI)를 상기 수지 고형분 대비 7 중량부, 디부틸틴디라우레이트(Dibutyl Tin Dilaurate, DBTDL) 30ppm을 넣고, 50℃~55℃에서 8 시간 반응시켜 2-이소시아네이토에틸 메타크릴레이트 모노머의 이소시아네이트 기가 아크릴계 바인더의 수산기와 반응하여 FT-IR상에서 없어짐을 반응의 종말점으로 하였다. 메틸에틸케톤을 넣어 냉각시켜, 고형분 15% 바인더 수지를 제조하였다.7 parts by weight of methacryloyloxyethyl isocyanate (MOI) to the above-mentioned resin solids, Dibutyl Tin Dilaurate (DBTDL) 30ppm was added to the acrylic polyol binder prepared above, and 50 ° C to 55 ° C. The reaction was carried out for 8 hours at, and the isocyanate group of the 2-isocyanatoethyl methacrylate monomer reacted with the hydroxyl group of the acrylic binder to disappear on the FT-IR as the end point of the reaction. Methyl ethyl ketone was added and cooled to prepare a 15% solids binder resin.
제조예 4: 바인더 수지의 제조Preparation Example 4 Preparation of Binder Resin
상기 제조예 1에서 상기 MOI를 반응시키지 않고 헥실 이소시아네이트(Hexyl isocyanate)를 반응시킨 것을 제외하고는 동일한 방법으로 바인더 수지를 제조하였다.A binder resin was prepared in the same manner as in Preparation Example 1, except that hexyl isocyanate was reacted without reacting the MOI.
상기 제조예 1　내지 4의 바인더 수지의 구체적인 사양은 하기 표 1과 같다.Specific specifications of the binder resin of Preparation Examples 1 to 4 are shown in Table 1 below.
표 1
　 제조예1 제조예2 제조예3 제조예4
중합법 현탁중합 현탁중합 현탁중합 현탁중합
아크릴계바인더함량 BA 45 54 62 54
EA 27 13 0 13
AN 18 18 18 18
HEMA 10 15 20 15
MOI 7 7 7 -
Hexylisocyanate - - - 7
바인더수지 　 바인더A 바인더B 바인더C 바인더D
Mw(g/mol) 670,000 610,000 530,000 600,000
PDI 2.5 2.6 2.8 2.6
Tg(℃) 3.1 3.2 3.5 3.1
Table 1
Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4
Polymerization Suspension polymerization Suspension polymerization Suspension polymerization Suspension polymerization
Acrylic binder content BA 45 54 62 54
EA 27 13 0 13
AN 18 18 18 18
HEMA 10 15 20 15
MOI 7 7 7 -
Hexylisocyanate - - - 7
Binder Resin Binder A Binder B Binder C Binder D
Mw (g / mol) 670,000 610,000 530,000 600,000
PDI 2.5 2.6 2.8 2.6
Tg (℃) 3.1 3.2 3.5 3.1
실시예 및 비교예Examples and Comparative Examples
하기 표 2에 기재된 바인더 수지 100 중량부에 대하여, 개시제 TPO(디페닐 (2,4,6-트리메틸벤조일)-포스핀 옥시드) 3 중량부를 용제 메틸에틸케톤에서 혼합하여 고형분 15 중량% 함량으로 충진제용 접착 필름 조성물을 제조하였다. 기재로 폴리에틸렌테레프탈레이트 필름에 코팅하고, 80℃~100℃에서 10 분 동안 건조시켜 충진제용 접착 필름(두께: 20㎛)을 제조하였다.To 100 parts by weight of the binder resin shown in Table 2, 3 parts by weight of the initiator TPO (diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide) was mixed in a solvent methyl ethyl ketone to a solid content of 15% by weight. An adhesive film composition for filler was prepared. The substrate was coated on a polyethylene terephthalate film and dried at 80 ° C. to 100 ° C. for 10 minutes, thereby preparing a filler adhesive film (thickness: 20 μm).
　
상기 실시예와 비교예에서 제조한 충진제용 접착 필름에 대해 하기의 물성을 평가하고 그 결과를 하기 표 2에 나타내었다.The following physical properties of the filler adhesive film prepared in Examples and Comparative Examples were evaluated and the results are shown in Table 2 below.
1. 잔류 모노머 함량(ppm): 접착 필름 1.0g을 350mJ/cm2　조건에서 경화시킨 후　샘플을 0.2g 내지 0.3g 칭량하여 클로로포름(CHCl3)과 같은 분석용 용매 9ml를 넣고 약 10 시간 이상 shaker로 용해시킨다. Internal standard 용액 1ml를 정확히 측량하여 넣고 잘 교반한 후 filter로 여과한다. GC 장비(장비명: HP-6890)로 분석하여 각 모노머 성분(BA, EA, AN 및 HEMA 등)과 Internal standard 의 농도비와 면적비를 plotting하고 각 성분의 직선상 관계수(r2)와 기울기(a) 그리고 절편(b)를 구하여(즉, y=ax+b), 검출되는 저분자 물질인 잔류 모노머 및 기타 검출물질의 유무 및 함량을 확인한다.1. Residual monomer content (ppm): After curing 1.0g of the adhesive film under 350mJ / cm 2 condition, weigh the sample from 0.2g to 0.3g, add 9ml of analytical solvent such as chloroform (CHCl 3 ) and shaker for about 10 hours. To dissolve. Accurately measure 1 ml of internal standard solution, stir well, and filter with filter. Analyze with GC equipment (device name: HP-6890) and plot the concentration ratio and area ratio of each monomer component (BA, EA, AN and HEMA, etc.) and internal standard, and the linear relationship coefficient (r2) and slope (a) of each component ) And then determine the presence or absence and content of the remaining monomers and other detection substances, which are small molecules, to be detected (ie y = ax + b).
2. 점착성(tackiness)(gf): 제조한 충진제용 접착 필름을 경화시키지 않고 프로브 택 측정기(probe tack tester; tacktoc-2000)로 점착성(tackiness)을 측정한 결과를 하기 표 2에 나타내었다. 측정방법은 ASTM D2979-71에 의거하여 깨끗한 프로브(Diameter=12.5mm)을 10+0.1mm/sec의 속도와 9.79+1.01kPa의 접촉 하중으로 1.0+0.01초 동안 점착제와 접촉시킨 다음 떼었을 때 필요한 최대 힘을 점착성(tackiness)값으로 하였다.2. Tackiness (gf): The result of measuring the tackiness with a probe tack tester (tacktoc-2000) without curing the prepared adhesive film for the filler is shown in Table 2 below. The measuring method is required according to ASTM D2979-71 when a clean probe (Diameter = 12.5mm) is contacted with the adhesive for 1.0 + 0.01 seconds at a speed of 10 + 0.1mm / sec and a contact load of 9.79 + 1.01kPa and then released. The maximum force was taken as the tackiness value.
3. Dark Spot 측정(신뢰성 평가): ITO 기판의 투명 전극의 상부에 정공 수송 층 및 유기 EL층을 0.05㎛의 두께로 순차 성막했다. 더욱이, 상기 유기 EL층의 상부에 배면 전극을 0.2㎛의 두께로 성막했다. 이러한 소자의 성막을 끝낸 후, 유리 기판상에 시트 상으로 형성된 상기 라미네이터를 이용해 합지하였으며, 이 전사한 유리 기판 위에 유리기판을 겹치고, 진공 라미네이타를 이용해 가열 압착시켰다. 그 후, 각 시료에 자외선을 350mJ/cm2 조사하여 광경화를 시켰다. 이와 같이 해 패널을 작성해, 초기의 Dark Spot의 발생과, 85℃, 85%, 1000 시간의 신뢰성 조건 방치했을 때의 Dark Spot의 성장을 관찰했다. 관찰 방법은 광학 현미경에 의한 평가 기준은 다음과 같이 진행하였다.3. Dark spot measurement (reliability evaluation): The positive hole transport layer and the organic electroluminescent layer were formed into a film at 0.05 micrometer thickness in order on the transparent electrode of an ITO substrate. Furthermore, a back electrode was formed into a film of 0.2 micrometer thickness on the said organic electroluminescent layer. After the film formation of such a device was finished, the laminate was laminated using the laminator formed on the glass substrate in the form of a sheet. The glass substrate was laminated on the transferred glass substrate and heated and pressed using a vacuum laminator. Thereafter, each sample was irradiated with 350 mJ / cm 2 of ultraviolet rays to cause photocuring. In this way, a panel was prepared and observed for the occurrence of the initial dark spot and growth of the dark spot when left at 85 ° C, 85%, and 1000 hours of reliability conditions. As for the observation method, the evaluation criteria by an optical microscope advanced as follows.
* 초기 Dark Spot 발생평가: 직경 20 ㎛이상의 것이 확인되지 않았던 경우, 확인되었을 경우를 불합격으로 평가함.* Initial Dark Spot Incidence Evaluation: When it was not confirmed that the diameter was 20 µm or more, it was evaluated as failing.
* 신뢰성 조건에서 Dark Spot 발생평가: 신뢰성 조건 1000 시간(hr) 경과 후에 직경 100 ㎛ 이상의 것이 확인되지 않았던 경우를 합격, 확인되었을 경우를 불합격으로 평가함.* Dark spot occurrence evaluation under reliability conditions: Passed and confirmed cases where the diameter of 100 µm or more was not confirmed after 1000 hours (hr) of reliability conditions were evaluated as fail.
표 2
Figure PCTKR2013010011-appb-T000001
 TABLE 2
Figure PCTKR2013010011-appb-T000001
* N.D: 검출되지 않음* N.D: not detected
상기 표 2에서 나타난 바와 같이, 본 발명의 유기발광소자용 충진제는 점착성이 좋아 기판에 쉽게 접착될 수 있다. 또한, 본 발명의 유기발광소자용 충진제는 경화 후에도 잔류 모노머가 검출되지 않았으며 다크 스폿이 발생하지 않음으로 신뢰성이 좋은 충진제로 사용될 수 있다.As shown in Table 2, the filler for the organic light emitting device of the present invention can be easily adhered to the substrate with good adhesion. In addition, the filler for the organic light emitting device of the present invention can be used as a reliable filler because no residual monomer is detected after curing and no dark spots occur.
반면에, 측쇄에 경화성 작용기가 없는 아크릴계 바인더를 포함하는 비교예 1의 접착 필름은 가교 전에는 점착성이 좋지만, 경화 후에는 가교를 할 수 없어 dark spot이 발생되어 신뢰성이 좋지 않았다.On the other hand, the adhesive film of Comparative Example 1 containing an acrylic binder having no curable functional group in the side chain had good adhesiveness before crosslinking, but was unable to crosslink after curing, resulting in dark spots and poor reliability.
　
본 발명은 상기 실시예 및 도면에 의해 한정되는 것이 아니라 서로 다른 다양한 형태가 될 수 있고, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 것이다. 그러므로, 이상에서 기술한 실시예와 도면은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야 한다.The present invention is not limited to the above embodiments and drawings, but may be in various forms, and a person skilled in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that it may be implemented in a form. Therefore, it is to be understood that the embodiments and drawings described above are exemplary in all respects and not restrictive.

Claims (17)

  1. 측쇄에 경화성 작용기를 갖는 바인더 수지 및 개시제를 포함하는 유기발광소자용 충진제.Filler for organic light emitting elements containing binder resin and initiator which have a curable functional group in a side chain.
  2. 제1항에 있어서, 상기 경화성 작용기는 (메타)아크릴레이트기, 비닐기 및 에폭시기 중 하나 이상을 포함하는 유기발광소자용 충진제.The filler of claim 1, wherein the curable functional group comprises at least one of a (meth) acrylate group, a vinyl group, and an epoxy group.
  3. 제1항에 있어서, 상기 경화성 작용기는 상기 바인더 수지 중 약 1 중량% 내지 약 10 중량%로 포함되는 유기발광소자용 충진제.The filler of claim 1, wherein the curable functional group is included in about 1% by weight to about 10% by weight of the binder resin.
  4. 제1항에 있어서, 상기 바인더 수지는 수산기를 갖는 고분자 수지와 반응성 작용기를 갖는 (메타)아크릴계 화합물을 반응시켜 형성되는 유기발광소자용 충진제.The filler of claim 1, wherein the binder resin is formed by reacting a polymer resin having a hydroxyl group with a (meth) acrylic compound having a reactive functional group.
  5. 제4항에 있어서, 상기 고분자 수지는 알킬기, 수산기 및 니트릴기를 갖는 (메타)아크릴계 바인더를 포함하는 유기발광소자용 충진제.The organic light emitting diode filler of claim 4, wherein the polymer resin comprises a (meth) acrylic binder having an alkyl group, a hydroxyl group, and a nitrile group.
  6. 제4항에 있어서, 상기 고분자 수지는 알킬기를 갖는 (메타)아크릴계 단량체, 니트릴기를 갖는 (메타)아크릴계 단량체 및 수산기를 갖는 (메타)아크릴계 단량체를 포함하는 단량체 혼합물의 공중합체를 포함하는 유기발광소자용 충진제.The organic light emitting device of claim 4, wherein the polymer resin comprises a copolymer of a (meth) acrylic monomer having an alkyl group, a (meth) acrylic monomer having a nitrile group, and a monomer mixture including a (meth) acrylic monomer having a hydroxyl group. Fillers.
  7. 제6항에 있어서, 상기 공중합체는 현탁 중합에 의해 형성되는 유기발광소자용 충진제.The filler of claim 6, wherein the copolymer is formed by suspension polymerization.
  8. 제4항에 있어서, 상기 (메타)아크릴계 화합물은 (메타)아크릴로일옥시알킬 이소시아네이트를 포함하는 유기발광소자용 충진제.The filler for an organic light emitting device according to claim 4, wherein the (meth) acrylic compound comprises (meth) acryloyloxyalkyl isocyanate.
  9. 제4항에 있어서, 상기 바인더 수지는 상기 고분자 수지 약 90 중량% 내지 약 99 중량% 및 상기 (메타)아크릴계 화합물 약 1 중량% 내지 약 10 중량%를 반응시킨 유기발광소자용 충진제.The filler of claim 4, wherein the binder resin is reacted with about 90% by weight to about 99% by weight of the polymer resin and about 1% by weight to about 10% by weight of the (meth) acrylic compound.
  10. 제1항에 있어서, 상기 바인더 수지는 다분산도가 약 2.0 내지 약 3.0인 유기발광소자용 충진제.The filler of claim 1, wherein the binder resin has a polydispersity of about 2.0 to about 3.0.
  11. 제1항에 있어서, 상기 바인더 수지는 하기 화학식 1의 말단을 갖는 유기발광소자용 충진제:According to claim 1, wherein the binder resin is a filler for an organic light emitting device having a terminal of the formula (1):
    <화학식 1><Formula 1>
    * - (CH2)n - O - C(=O) - NH - (CH2)m - X*-(CH 2 ) n -O-C (= O)-NH-(CH 2 ) m -X
    (상기에서, *는 상기 바인더 수지의 주쇄에 대한 연결 부위이고,(In the above, * is a linking site to the main chain of the binder resin,
    X는 아크릴레이트기 또는 메타크릴레이트기이고,X is an acrylate group or a methacrylate group,
    n, m은 동일하거나 다르고, 1~6의 정수이다).n and m are the same or different and are integers of 1 to 6).
  12. 제1항에 있어서, 상기 충진제는 상기 바인더 수지 약 90 중량% 내지 약 98 중량% 및 상기 개시제 약 2 중량% 내지 약 10 중량%를 포함하는 유기발광소자용 충진제.The filler of claim 1, wherein the filler comprises about 90 wt% to about 98 wt% of the binder resin and about 2 wt% to about 10 wt% of the initiator.
  13. 제1항에 있어서, 상기 충진제는 필름 형태를 갖는 유기발광소자용 충진제.The filler of claim 1, wherein the filler has a film form.
  14. 제13항에 있어서, 상기 필름은 두께가 약 5㎛　내지 약　40㎛인 유기발광소자용 충진제.The filler of claim 13, wherein the film has a thickness of about 5 μm to about 40 μm.
  15. 제1항 내지 제14항 중 어느 한 항의 유기발광소자용 충진제의 경화물을 충진제로 포함하는 유기발광장치.An organic light emitting device comprising a cured product of the filler for an organic light emitting device according to any one of claims 1 to 14 as a filler.
  16. 제15항에 있어서, 상기 유기발광장치는 제1 기판; 상기 제1 기판과 대향하도록 배치된 제2 기판; 상기 제1 기판 상부에 형성된 유기발광소자; 상기 유기발광소자를 덮고 상기 제1 기판과 상기 제2 기판 사이의 공간을 충진하는 상기 충진제를 포함하는 유기발광장치.The method of claim 15, wherein the organic light emitting device comprises: a first substrate; A second substrate disposed to face the first substrate; An organic light emitting diode formed on the first substrate; An organic light emitting device comprising the filler to cover the organic light emitting device and to fill the space between the first substrate and the second substrate.
  17. 제15항에 있어서, 상기 유기발광장치는 실링재를 더 포함하는 유기발광장치.The organic light emitting device of claim 15, wherein the organic light emitting device further comprises a sealing material.
PCT/KR2013/010011 2013-01-11 2013-11-06 Filler for organic light emitting diodes and organic light emitting device comprising same WO2014109469A1 (en)

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KR1020130003679A KR101542623B1 (en) 2013-01-11 2013-01-11 Filling agent for organic light emitting diode and organic light emitting diode apparatus comprising the same

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KR20100058889A (en) * 2008-11-25 2010-06-04 금호석유화학 주식회사 Curable resin composition, flat panel display having cured product from the same and method of manufacturing flat panel display
KR20100063235A (en) * 2008-12-03 2010-06-11 엘지디스플레이 주식회사 Organic light emitting display device and method for fabricating the same
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KR20110001884A (en) * 2009-06-29 2011-01-06 주식회사 동진쎄미켐 Photocurable resin compositon for sealing of optical device
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