WO2015046740A1 - Photocurable resin composition for donor film and donor film - Google Patents

Photocurable resin composition for donor film and donor film Download PDF

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WO2015046740A1
WO2015046740A1 PCT/KR2014/007159 KR2014007159W WO2015046740A1 WO 2015046740 A1 WO2015046740 A1 WO 2015046740A1 KR 2014007159 W KR2014007159 W KR 2014007159W WO 2015046740 A1 WO2015046740 A1 WO 2015046740A1
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acrylate
resin composition
photocurable resin
donor
compound
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PCT/KR2014/007159
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French (fr)
Korean (ko)
Inventor
최태이
조명현
김장순
배효대
윤경준
김수진
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(주)엘지하우시스
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Publication of WO2015046740A1 publication Critical patent/WO2015046740A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • It relates to a photocurable resin composition for donor films and a donor film.
  • OLED organic light emitting display device
  • the method of forming an organic film layer on an OLED includes a deposition method, an inkjet method, a laser thermal transfer method (LITI), and the like.
  • the organic film layer composition including an additive or a surfactant is coated on a substrate having a relatively low surface energy in order to form an organic film layer in the OLED, there is a problem in that the wettability is poor and the coating property is low.
  • it may cause thermal damage to the organic film layer there is a problem that the phase difference of the organic film layer due to post-curing.
  • One embodiment of the present invention provides a photocurable resin composition for a donor film excellent in patterning reliability and transfer quality.
  • Another embodiment of the present invention provides a donor film including an intermediate layer formed from a photocurable resin composition for a donor film having excellent patterning reliability and transfer quality.
  • a photocurable resin composition for a donor film the glass transition temperature of the cured product of the composition is about 40 °C to about 180 °C, storage modulus is from about 3.5 to about 5.5 GPa at 25 °C Can be.
  • the composition is at least one acrylate monomer selected from the group consisting of urethane acrylates, epoxy acrylates, ester acrylates, cardo-based acrylates, and combinations thereof, acrylate oligomers, It may include a photocurable compound, a crosslinkable acrylate monomer and a photoinitiator including an acrylate prepolymer or a combination thereof.
  • the urethane acrylate is formed by polymerization of an isocyanate monomer and a polyol, and the isocyanate compound includes at least one or more selected from aliphatic isocyanate compounds, aromatic isocyanate compounds, and combinations thereof, and the polyol (meth) ) Acrylic acid hydroxyalkyl ester compound.
  • the epoxy acrylate may include at least one or more selected from bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (meth) acrylic acid adducts of phenol novolac epoxy resins, and combinations thereof. .
  • the ester acrylate may include a polyfunctional polyester acrylate compound of a polyhydric alcohol.
  • the cardo-based acrylate may be a compound to which photocurable acrylate is given by reacting a cardo-based compound of Formula 1 with at least one selected from the group consisting of dianhydride compounds, diol compounds, diacrylic acid, and combinations thereof.
  • R 1 and R 2 are each independently —OH, —NH 2 , —O—CH 2 —CH 2 —OH, or —COOH.
  • the photocurable compound may include about 30 to about 70% by weight.
  • It may include about 20 to about 60% by weight of the crosslinkable acrylate monomer.
  • the crosslinkable acrylate monomer may be two to four acrylate functional group-containing monomers.
  • the glass transition temperature (Tg) of the photocurable compound may be about -50 °C to about 60 °C.
  • the glass transition temperature of the cured product may be prepared to be about 40 ° C to about 180 ° C.
  • the photocurable resin composition for a donor film may include a photocurable compound comprising a weight average molecular weight of about 500 to about 20000 of an oligomer and a monomer in a ratio of about 1: 4 to about 4: 1.
  • the monomer may be an aliphatic group-containing monomer
  • the oligomer may be an aromatic group-containing oligomer
  • a substrate layer, a photothermal conversion layer and an intermediate layer provides a donor film which is a layer prepared by curing the photocurable resin composition for a donor film.
  • a transfer layer may be stacked on the intermediate layer.
  • the base film is glass; Or a transparent film including at least one selected from the group consisting of polyester, polycarbonate, polyolefin, polyvinyl, and combinations thereof.
  • the intermediate layer may have a surface energy of about 11 mN / m to about 21 mN / m.
  • the photocurable resin composition for donor film is excellent in patterning reliability and transfer quality.
  • the thermal expansion occurs well by adjusting the modulus of the intermediate layer, and the glass transition temperature is adjusted to optimize the deformation and swelling of the intermediate layer at the thermal expansion temperature.
  • FIG. 1 is a schematic cross-sectional view of a donor film according to an embodiment of the present invention.
  • any configuration is formed on the “top (or bottom)" of the substrate or “top (or bottom)” of the substrate means that any configuration is formed in contact with the top (or bottom) of the substrate.
  • it is not limited to not including other configurations between the substrate and any configuration formed on (or under) the substrate.
  • the photocurable resin composition for a donor film has a glass transition temperature of about 40 ° C to about 180 ° C of the cured product formed from the composition, and a storage modulus of the cured product of the composition is about 25 ° C. At about 3.5 to about 5.5 GPa.
  • the photocurable resin composition for a donor film is a composition for forming an intermediate layer interposed between a photothermal conversion layer and a transfer layer of a donor film, and the intermediate layer is formed to have the above-described glass transition temperature and storage modulus characteristics.
  • a donor film including an intermediate layer formed from the photocurable resin composition for donor film By using a donor film including an intermediate layer formed from the photocurable resin composition for donor film, it is possible to improve the performance of transferring the organic material of the transfer layer during patterning using laser thermal transfer.
  • the organic material After depositing an organic material on the donor film to form a transfer layer, the organic material is transferred to a substrate to be transferred by laser patterning.
  • the intermediate layer formed from the photocurable resin composition for the donor film has a glass transition temperature of less than about 40 ° C., a problem may occur that the stability and storage properties of the film are deteriorated at room temperature, and when the glass transition temperature exceeds about 180 ° C., the laser When the thermal transfer is performed, the intermediate layer may be maintained in a glassy state, which may cause a problem in that transfer performance is degraded.
  • the cured intermediate layer from the UV-curable resin composition for the donor film has a storage modulus of less than about 3.5 GPa, organic transfer may occur to areas that should not be patterned when performing laser thermal transfer, thereby causing a problem of lowering patterning reliability. If the storage modulus exceeds about 5.5 GPa, thermal expansion by the laser in the intermediate layer may be difficult to occur during laser thermal transfer.
  • the photocurable resin composition for a donor film is specifically, at least one selected from the group consisting of urethane acrylates, epoxy acrylates, ester acrylates, cardo-based acrylates, and combinations thereof.
  • a photocurable compound including an acrylate monomer, an acrylate oligomer, an acrylate prepolymer, or a combination thereof may further include additives such as a crosslinkable acrylate monomer and a photoinitiator.
  • the acrylate oligomer of the photocurable compound may have a weight average molecular weight of about 500 to about 20000.
  • the photocurable resin composition for a donor film may include about 20 to about 60 wt% of the aforementioned acrylate oligomer as the photocurable compound.
  • the urethane acrylate is to give an acrylate group to the urethane compound to be UV cured, it is a generic name of a compound having a urethane bond and an acrylate group.
  • the urethane bond may be formed by polymerizing an isocyanate monomer and a polyol.
  • the urethane acrylate photocurable oligomer may be a urethane bond formed by reacting an isocyanate compound with a (meth) acrylic acid hydroxyalkyl ester compound. It may include an oligomer formed by polymerizing a weight average molecular weight of about 500 to about 20000.
  • isocyanate compounds include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), or toluene diisocyanate (TDI), and methylene diphenyl diisocyanate.
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • methylene diphenyl diisocyanate methylene diphenyl diisocyanate
  • Aromatic isocyanate compounds such as isocyanate (methylene diphenyl diisocyanate, MDI), etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • (meth) acrylic acid hydroxyalkyl ester compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and the like, and combinations thereof This can be used.
  • the epoxy acrylate is a compound in which an acrylate group is given to an epoxy group-containing epoxy group compound as a photocurable compound, and specific examples thereof include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or a phenol novolak epoxy resin. Epoxy acrylate type compounds etc. which are the (meth) acrylic acid addition products of these are mentioned.
  • the ester acrylate is a compound in which an acrylate group is added to an ester compound as a photocurable compound, and specific examples thereof include polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate. It may be a polyfunctional polyester acrylate compound.
  • the cardo-based acrylate (or fluorene-based acrylate) is a photocurable compound, specifically, at least one selected from the group consisting of a cardo-based compound of Formula 1, a dianhydride compound, a diol compound, diacrylic acid, and a combination thereof It may be a compound endowed with a photocurable acrylate by reacting one.
  • R 1 and R 2 are each independently —OH, —NH 2 , —O—CH 2 —CH 2 —OH, or —COOH.
  • the photocurable composition for a donor film may include about 30 to about 70% by weight of the photocurable compound.
  • crosslinkable acrylate monomer various photocurable monomers may be used, for example, 2 to 4 acrylate functional group-containing monomers.
  • specific examples of the crosslinkable acrylate monomer include 1,2-ethylene glycol diacrylate, 1,12-dodecanediol acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid ) Neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (Meth) acryloxy ethyl is
  • the photocurable resin composition for a donor film may include about 20 to about 60 wt% of the crosslinkable acrylate monomer.
  • the photoinitiator examples include benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, ⁇ , ⁇ -methoxy- ⁇ -hydro Roxacytophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, oxime ester system And one or more selected from the group consisting of.
  • the UV curable resin composition for a donor film may include about 0.1 to about 10% by weight of the photoinitiator.
  • an oligomeric raw material prepared as the photocurable compound
  • the glass transition temperature of the range of about -50 °C to about 60 °C, and after forming a cured polymer network structure through a photoinitiator can be prepared so that the glass transition temperature of the cured product is about 40 °C to about 180 °C.
  • isocyanate and (meth) acrylic acid hydroxyalkyl ester include an aromatic group to give a hard repeating unit
  • the glass transition temperature can be raised.
  • the photocurable resin composition for a donor film can be adjusted by changing the type, molecular weight, content, etc. of the monomer constituting a repeat unit of the photocurable compound in order to implement the storage modulus of the above-described numerical range have.
  • the storage modulus increases if the repeating unit consists of an aromatic of hard type.
  • it is also possible to control the storage modulus through the molecular weight when the molecular weight is large, the interval between the curing sites (site) is long and the crosslinking density (crosslinking density) is lowered, which results in a decrease in the storage modulus.
  • the photocurable resin composition for a donor film may include a content ratio of oligomer and monomer having a weight average molecular weight of about 500 to about 20000 to about 1: 4 to about 4: 1, specifically, the monomer It may be an aliphatic group-containing monomer, the oligomer may be an aromatic group-containing oligomer.
  • the aliphatic monomer and the aromatic monomer may not be included at the same time.
  • the photocurable resin composition for a donor film is from the group consisting of a crosslinking agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, a plasticizer, and combinations thereof in a range that does not affect the effect of the invention. It may further comprise one or more additives selected.
  • a donor film including a substrate layer, a photothermal conversion layer, an intermediate layer, and a transfer layer.
  • middle layer is manufactured by hardening
  • the donor film may improve the performance of transferring the organic material of the transfer layer during patterning using laser thermal transfer.
  • Patterning is one of the factors that determine the transfer quality, so that thermal expansion occurs well by adjusting the storage modulus of the intermediate layer formed from the photocurable resin composition for a donor film described above, and controlling the glass transition temperature to deform and swell the intermediate layer at the thermal expansion temperature.
  • the donor film may be usefully used for manufacturing a display device such as an organic light emitting display device.
  • the donor film 10 includes a base layer 11, a photothermal conversion layer 12 formed on the base layer 11, and an intermediate layer 13 formed on the photothermal conversion layer 12. do.
  • a transfer layer 14 formed on the intermediate layer 13 may be formed.
  • the base film 11 is glass; Or a transparent film including at least one selected from the group consisting of polyester, polycarbonate, polyolefin, polyvinyl, and combinations thereof.
  • the base film 11 is specifically, a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film, and the base film of the material is most preferable in view of processability, thermal stability and transparency. Do.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the surface of the base film 11 is modified by a surface treatment known to those skilled in the art, for example, a surface treatment such as corona, plasma, and the like to control adhesion, surface tension, etc. when the photothermal conversion layer 12 is laminated in a subsequent process. It is also possible.
  • the donor film 10 may further include a primer layer (not shown) formed on the base film 11.
  • a primer layer may be formed between the base film 11 and the photothermal conversion layer 12.
  • the primer layer is to control the temperature transfer between the base film and the adjacent layer, to improve the adhesion between the base film 11 and the adjacent layer, and to control the image forming radiation transfer to the photothermal conversion layer 12. If the primer layer is not formed, a phenomenon in which the base film 11 and the photothermal conversion layer 12 are separated in a transfer process using a laser may occur.
  • At least one selected from the group consisting of acrylic resins, polyurethane resins, polyester resins, and combinations thereof may be used.
  • the base film 11 and the photothermal conversion layer 12 may be separated in a transfer process using a laser.
  • the photothermal conversion layer 12 is a layer that absorbs light in the infrared-visible ray region and converts a part of the light into heat, and is made of a resin composition including a thermosetting resin and a photothermal conversion material.
  • the intermediate layer 13 may be formed by coating the above-mentioned photocurable resin composition for a donor film and thermosetting or photocuring, wherein the intermediate layer 13 is transferred by a heat generated in the photothermal conversion layer 12.
  • the intermediate layer 13 is excellent in patterning reliability as described above.
  • the intermediate layer 13 preferably has a low surface energy. Since the intermediate layer 13 has a low surface energy, there is an advantage in that the organic material is easily transferred even in a small thermal expansion.
  • the intermediate layer 13 may have a surface energy of about 11 mN / m to about 21 mN / m.
  • the intermediate layer 13 may be formed to have a thickness of, for example, about 1 ⁇ m to about 5 ⁇ m. When the thickness of the intermediate layer 13 is less than about 1 ⁇ m, the organic material of the transfer layer may be damaged due to the heat generated in the photothermal conversion layer. If the thickness of the intermediate layer 13 is greater than about 5 ⁇ m, the transfer performance may not be sufficiently swelled.
  • the transfer layer 14 typically includes one or more layers for transferring to the receptor.
  • it may be formed using organic, inorganic, organometallic and other materials, including electroluminescent materials or electrically active materials.
  • poly (phenylenevinylene), poly-para-phenylene, polyfluorene, polydialkylfluorene, polythiophene, poly (9-vinylcarbazole), poly (N-vinylcarbazole-vinyl Alcohol) copolymers, triarylamine, polynorbornene, polyaniline, polyarylpolyamine, triphenylamine-polyetherketone and the like can be used.
  • the transfer layer 14 may further include one or more materials selected from known light emitting materials, hole transporting organic materials, and electron transporting organic materials so as to match the characteristics of the organic light emitting device to be manufactured. It may include a compound comprising at least one of a non-luminescent low molecular material, a non-luminescent charge transfer polymer material and a curable organic semi-inder material.
  • a photocurable resin composition was prepared by mixing 50 wt% of a photocurable compound (weight average molecular weight 3000) of a cardo-based acrylate having an aromatic group, 45 wt% of a bifunctional acrylate monomer having an aliphatic group, and 5 wt% of a photoinitiator.
  • UV lamp After forming a photothermal conversion layer containing a carbon black photothermal conversion material on the substrate layer of the polyester film to a thickness of 3 ⁇ m, and coating the urethane acrylate-based resin composition prepared above to a thickness of 3 ⁇ m, UV lamp The donor film was manufactured by preparing an intermediate layer by irradiating with UV and curing.
  • the cardo-based acrylate is a hard type oligomer (molecular weight 3000) having a hard structure in which an aromatic 5-membered ring and a 6-membered ring cross each other, and the composition combining the bifunctional monomer in the content ratio may realize a storage modulus within a desired range. .
  • the glass transition temperature and storage modulus of the prepared intermediate layer were measured.
  • the photocurable resin composition was prepared to contain 60 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 35 wt% of the bifunctional acrylate monomer, and 5 wt% of the photoinitiator.
  • a donor film was produced by the method.
  • the photocurable resin composition was the same as in Example 1 except that the photocurable resin composition was prepared to contain 75 wt% of urethane acrylate (weight average molecular weight 6000) having an aromatic constituent, 20 wt% of a bifunctional acrylate monomer, and 5 wt% of a photoinitiator.
  • a donor film was produced by the method.
  • the photocurable resin composition was prepared to contain 80 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 15 wt% of bifunctional acrylate monomer, and 5 wt% of a photoinitiator.
  • the donor film was prepared by the following.
  • the photocurable resin composition was prepared to contain 30 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 65 wt% of bifunctional acrylate monomer, and 5 wt% of a photoinitiator.
  • the donor film was prepared by the following.
  • the photocurable resin composition was prepared to contain 50 wt% of epoxy acrylate (weight average molecular weight 3000) having an aliphatic constituent, 45 wt% of trifunctional acrylate monomer, and 5 wt% of a photoinitiator.
  • the donor film was prepared by the following.
  • Nanoindentation Hysitron TI750: Measured at room temperature in nanoDMA mode to obtain a storage modulus value.
  • the transfer quality was evaluated by the following method.
  • Test pattern substrate preparation A test pattern substrate having a bank structure thickness of 0.5 ⁇ m or less and a Taper Angle of 15 ° or less is prepared.
  • Organic DNTPD N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4 on a test pattern substrate having a pixel size of 11 ⁇ 78 ⁇ m , 4'-diamine was deposited to 100 mm thick.
  • Example 2 2) TCTA ((N-carbazolyl) -triphenylamine) was deposited on the film surface prepared in Example 1-2 and Comparative Example 1-2 to a thickness of 500 mm 3.
  • a mask is mounted to allow imaging with alignment with the pixel area of the substrate.
  • the laser beam is irradiated with an amount of energy of 1.5 J / cm 2 onto the substrate (PET surface) of the prepared sample and scanned.
  • Example 1-2 After scanning After removal of the donor film in Example 1-2 and Comparative Example 1-2, the organic transfer traces to the substrate surface is evaluated using an optical microscope.

Abstract

Provided is a photocurable resin composition for a donor film, wherein a cured product from the composition has a glass transition temperature of approximately 40 to 180℃, and a storage modulus of approximately 3.5 to approximately 5.5 GPa at approximately 25℃.

Description

도너 필름용 광경화성 수지 조성물 및 도너 필름Photocurable resin composition and donor film for donor films
도너 필름용 광경화성 수지 조성물 및 도너 필름에 관한 것이다.It relates to a photocurable resin composition for donor films and a donor film.
최근 디스플레이 장치의 기술의 발전 동향은 에너지를 적게 이용하면서도 동시에 시인성이 뛰어난 기술의 개발이 요구되는 실정이다. 이에 따라 기존의 발광방식에 비해 에너지 소비가 적다고 알려진 유기발광표시장치(OLED)를 이용한 디스플레이 장치의 개발이 경쟁적으로 이루어지고 있는 상황이다.Recently, the trend of the development of display device technology requires the development of a technology that is excellent in visibility while using less energy. Accordingly, the development of a display device using an organic light emitting display device (OLED), which is known to consume less energy than a conventional light emitting method, is being made competitively.
이러한 OLED를 이용하는 디스플레이 장치의 풀컬러(full color)를 구현하기 위해서는 발광소자에 컬러를 패터닝(patterning)하는 방법이 매우 중요하며, 결과적으로는 발광소자의 색상을 결정하는 OLED의 유기막층을 형성하는 방법에 따라 구현 효과의 차이가 발생한다. OLED에 유기막층을 형성하는 방법에는 증착법, 잉크젯 방식, 레이저 열전사 방식(LITI) 등이 있다. In order to realize full color of the display device using the OLED, a method of patterning color on the light emitting device is very important, and as a result, forming an organic layer of the OLED that determines the color of the light emitting device. Depending on the method, the difference in implementation effect occurs. The method of forming an organic film layer on an OLED includes a deposition method, an inkjet method, a laser thermal transfer method (LITI), and the like.
OLED에 유기막층을 형성하기 위해 첨가제나 계면활성제를 포함하는 유기막층 조성물을 상대적으로 표면에너지가 낮은 기판에 코팅하는 경우, 젖음성이 좋지 않아 코팅성이 낮아지는 문제점이 있다. 또한, OLED에 유기막층을 형성하기 위해 기존의 열경화방식을 이용하는 경우, 유기막층의 열적 손상을 입힐 수 있으며, 사후 경화에 의한 유기막층의 위상차가 생기게 되는 문제점이 있다.When the organic film layer composition including an additive or a surfactant is coated on a substrate having a relatively low surface energy in order to form an organic film layer in the OLED, there is a problem in that the wettability is poor and the coating property is low. In addition, when using an existing thermosetting method to form an organic film layer in the OLED, it may cause thermal damage to the organic film layer, there is a problem that the phase difference of the organic film layer due to post-curing.
본 발명의 일 구현예는 패터닝 신뢰성 및 전사 품질이 우수한 도너 필름용 광경화형 수지 조성물을 제공한다.One embodiment of the present invention provides a photocurable resin composition for a donor film excellent in patterning reliability and transfer quality.
본 발명의 다른 구현예는 패터닝 신뢰성 및 전사 품질이 우수한 도너 필름용 광경화형 수지 조성물로부터 형성된 중간층을 포함하는 도너 필름을 제공한다.Another embodiment of the present invention provides a donor film including an intermediate layer formed from a photocurable resin composition for a donor film having excellent patterning reliability and transfer quality.
본 발명의 일 구현예에서, 도너 필름용 광경화형 수지 조성물을 제공하고, 상기 조성물의 경화물의 유리전이온도가 약 40℃ 내지 약 180℃이고, 저장 모듈러스는 25℃에서 약 3.5 내지 약 5.5 GPa일 수 있다.In one embodiment of the present invention, there is provided a photocurable resin composition for a donor film, the glass transition temperature of the cured product of the composition is about 40 ℃ to about 180 ℃, storage modulus is from about 3.5 to about 5.5 GPa at 25 ℃ Can be.
상기 조성물은 우레탄 아크릴레이트계, 에폭시 아크릴레이트계, 에스테르 아크릴레이트계, 카도계(cardo-based) 아크릴레이트계 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나의 아크릴레이트계 모노머, 아크릴레이트계 올리고머, 아크릴레이트계 프리폴리머 또는 이들의 조합을 포함하는 광경화성 화합물, 가교성 아크릴레이트계 모노머 및 광개시제를 포함할 수 있다.The composition is at least one acrylate monomer selected from the group consisting of urethane acrylates, epoxy acrylates, ester acrylates, cardo-based acrylates, and combinations thereof, acrylate oligomers, It may include a photocurable compound, a crosslinkable acrylate monomer and a photoinitiator including an acrylate prepolymer or a combination thereof.
상기 우레탄아크릴레이트는 이소시아네이트계 모노머와 폴리올이 중합반응하여 형성된 것으로, 상기 이소시아네이트계 화합물은 지방족 이소시아네이트계 화합물, 방향족 이소시아네이트계 화합물 및 이들의 조합으로부터 선택된 적어도 1종 이상을 포함하고, 상기 폴리올은 (메타)아크릴산히드록시알킬에스테르계 화합물일 수 있다.The urethane acrylate is formed by polymerization of an isocyanate monomer and a polyol, and the isocyanate compound includes at least one or more selected from aliphatic isocyanate compounds, aromatic isocyanate compounds, and combinations thereof, and the polyol (meth) ) Acrylic acid hydroxyalkyl ester compound.
상기 에폭시 아크릴레이트는 비스페놀 A 디글리시딜에테르, 수소 첨가 비스페놀 A 디글리시딜에테르, 페놀 노볼락 에폭시 수지의 (메트)아크릴산 부가물 및 이들의 조합으로부터 선택된 적어도 1종 이상을 포함할 수 있다.The epoxy acrylate may include at least one or more selected from bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (meth) acrylic acid adducts of phenol novolac epoxy resins, and combinations thereof. .
상기 에스테르 아크릴레이트는 다가 알코올의 다관능 폴리에스테르아크릴레이트계 화합물을 포함할 수 있다.The ester acrylate may include a polyfunctional polyester acrylate compound of a polyhydric alcohol.
상기 카도계 아크릴레이트는 하기 화학식 1의 카도계 화합물과 디안하이드라이드 화합물, 디올 화합물, 디아크릴산 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 반응시켜 광경화 가능한 아크릴레이트가 부여된 화합물일 있다.The cardo-based acrylate may be a compound to which photocurable acrylate is given by reacting a cardo-based compound of Formula 1 with at least one selected from the group consisting of dianhydride compounds, diol compounds, diacrylic acid, and combinations thereof.
[화학식 1][Formula 1]
Figure PCTKR2014007159-appb-I000001
Figure PCTKR2014007159-appb-I000001
상기 식에서, Where
R1 및 R2는, 각각 독립적으로, -OH, -NH2, -O-CH2-CH2-OH 또는 -COOH이다.R 1 and R 2 are each independently —OH, —NH 2 , —O—CH 2 —CH 2 —OH, or —COOH.
상기 광경화성 화합물 약 30 내지 약 70 중량% 포함할 수 있다.The photocurable compound may include about 30 to about 70% by weight.
상기 가교성 아크릴레이트 모노머를 약 20 내지 약 60 중량% 포함할 수 있다.It may include about 20 to about 60% by weight of the crosslinkable acrylate monomer.
상기 가교성 아크릴레이트 모노머는 2개 내지 4개의 아크릴레이트 관능기 함유 모노머일 수 있다.The crosslinkable acrylate monomer may be two to four acrylate functional group-containing monomers.
상기 광경화형 화합물의 유리전이온도(Tg)는 약 -50℃ 내지 약 60℃일 수 있다.The glass transition temperature (Tg) of the photocurable compound may be about -50 ℃ to about 60 ℃.
광개시제를 통해 경화된 고분자 네트워크 구조를 형성한 후 경화물의 유리전이 온도가 약 40℃ 내지 약 180℃가 되도록 제조된 것일 수 있다.After forming the cured polymer network structure through the photoinitiator, the glass transition temperature of the cured product may be prepared to be about 40 ° C to about 180 ° C.
상기 도너 필름용 광경화형 수지 조성물은 중량평균분자량 약 500 내지 약 20000인 올리고머와 모노머의 함량비가 약 1:4 내지 약 4:1이 되도록 포함하는 광경화성 화합물을 포함할 수 있다.The photocurable resin composition for a donor film may include a photocurable compound comprising a weight average molecular weight of about 500 to about 20000 of an oligomer and a monomer in a ratio of about 1: 4 to about 4: 1.
상기 모노머는 지방족기 함유 모노머이고, 상기 올리고머는 방향족기 함유 올리고머일 수 있다.The monomer may be an aliphatic group-containing monomer, and the oligomer may be an aromatic group-containing oligomer.
본 발명의 다른 구현예에서, 기재층, 광열변환층 및 중간층을 포함하고, 상기 중간층은 상기 도너 필름용 광경화성 수지 조성물을 경화시켜 제조된 층인 도너 필름을 제공한다.In another embodiment of the present invention, a substrate layer, a photothermal conversion layer and an intermediate layer, the intermediate layer provides a donor film which is a layer prepared by curing the photocurable resin composition for a donor film.
상기 중간층 상부에 전사층이 적층될 수 있다.A transfer layer may be stacked on the intermediate layer.
상기 기재필름은 유리; 또는 폴리에스테르, 폴리카보네이트, 폴리올레핀, 폴리비닐 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 투명 필름일 수 있다.The base film is glass; Or a transparent film including at least one selected from the group consisting of polyester, polycarbonate, polyolefin, polyvinyl, and combinations thereof.
상기 기재필름에 형성되는 프라이머층을 추가로 포함할 수 있다.It may further include a primer layer formed on the base film.
상기 중간층은 약 11 mN/m 내지 약 21 mN/m의 표면 에너지를 가질 수 있다.The intermediate layer may have a surface energy of about 11 mN / m to about 21 mN / m.
상기 도너 필름용 광경화형 수지 조성물은 패터닝 신뢰성 및 전사 품질이 우수하다. 패터닝의 전사품질을 결정하는 요소 중의 하나로 중간층의 모듈러스를 조절하여 열팽창이 잘 일어나도록 하며, 유리전이온도를 조절하여 열팽창 온도에서 중간층의 변형 및 부풀어오름을 최적화 하고자 한다. The photocurable resin composition for donor film is excellent in patterning reliability and transfer quality. As one of the factors that determine the transfer quality of patterning, the thermal expansion occurs well by adjusting the modulus of the intermediate layer, and the glass transition temperature is adjusted to optimize the deformation and swelling of the intermediate layer at the thermal expansion temperature.
도 1은 본 발명의 일 구현예에 따른 도너 필름의 개략적인 단면도이다.1 is a schematic cross-sectional view of a donor film according to an embodiment of the present invention.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.
본 발명을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 동일 또는 유사한 구성요소에 대해서는 동일한 참조 부호를 붙이도록 한다.In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification.
도면에서 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하여 나타내었다. 그리고 도면에서, 설명의 편의를 위해, 일부 층 및 영역의 두께를 과장되게 나타내었다.In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.
이하에서 기재의 “상부 (또는 하부)” 또는 기재의 “상 (또는 하)”에 임의의 구성이 형성된다는 것은, 임의의 구성이 상기 기재의 상면 (또는 하면)에 접하여 형성되는 것을 의미할 뿐만 아니라, 상기 기재와 기재 상에 (또는 하에) 형성된 임의의 구성 사이에 다른 구성을 포함하지 않는 것으로 한정하는 것은 아니다.Hereinafter, any configuration is formed on the "top (or bottom)" of the substrate or "top (or bottom)" of the substrate means that any configuration is formed in contact with the top (or bottom) of the substrate. However, it is not limited to not including other configurations between the substrate and any configuration formed on (or under) the substrate.
본 발명의 일 구현예에 따른 도너 필름용 광경화형 수지 조성물은 상기 조성물로부터 형성된 경화물의 유리전이온도가 약 40℃ 내지 약 180℃이고, 상기 조성물의 경화물의 저장 모듈러스 (storage modulus)은 약 25℃에서 약 3.5 내지 약 5.5 GPa로 구현할 수 있다.The photocurable resin composition for a donor film according to an embodiment of the present invention has a glass transition temperature of about 40 ° C to about 180 ° C of the cured product formed from the composition, and a storage modulus of the cured product of the composition is about 25 ° C. At about 3.5 to about 5.5 GPa.
상기 도너 필름용 광경화형 수지 조성물은 도너 필름의 광열변환층과 전사층 사이에 개재되는 중간층 형성용 조성물로서, 상기 중간층은 전술한 유리전이온도와 저장 모듈러스 특성을 갖도록 형성된다.The photocurable resin composition for a donor film is a composition for forming an intermediate layer interposed between a photothermal conversion layer and a transfer layer of a donor film, and the intermediate layer is formed to have the above-described glass transition temperature and storage modulus characteristics.
상기 도너 필름용 광경화형 수지 조성물로부터 형성된 중간층을 포함하는 도너 필름을 사용하여 레이저 열전사를 이용한 패터닝시 전사층의 유기물이 전사되는 성능을 개선시킬 수 있다.By using a donor film including an intermediate layer formed from the photocurable resin composition for donor film, it is possible to improve the performance of transferring the organic material of the transfer layer during patterning using laser thermal transfer.
도너 필름에서 유기물을 증착시켜 전사층을 형성한 후, 레이저 패터닝을 통해 증착된 유기물을 전사시키고자 하는 기재로 전사하게 된다. After depositing an organic material on the donor film to form a transfer layer, the organic material is transferred to a substrate to be transferred by laser patterning.
상기 도너 필름용 광경화형 수지 조성물로부터 형성된 중간층이 약 40℃ 미만의 유리전이온도를 가지면, 상온에서 필름의 안정성 및 저장성이 떨어지는 문제점이 발생할 수 있고, 약 180℃ 초과하는 유리전이온도를 가지면, 레이저 열전사 수행시 중간층이 유리 상태 (glassy state)로 유지되어 전사 성능이 떨어지는 문제점이 발생할 수 있다.If the intermediate layer formed from the photocurable resin composition for the donor film has a glass transition temperature of less than about 40 ° C., a problem may occur that the stability and storage properties of the film are deteriorated at room temperature, and when the glass transition temperature exceeds about 180 ° C., the laser When the thermal transfer is performed, the intermediate layer may be maintained in a glassy state, which may cause a problem in that transfer performance is degraded.
한편, 상기 도너 필름용 UV경화형 수지 조성물로부터 경화된 중간층이 약 3.5 GPa 미만의 저장 모듈러스를 가지면, 레이저 열전사 수행시 패터닝되지 않아야 되는 영역까지 유기물 전사가 일어나 패터닝 신뢰성을 저하하는 문제점이 발생할 수 있고, 약 5.5 GPa초과하는 저장 모듈러스를 가지면, 레이저 열전사 수행시 중간층에서 레이저에 의한 열팽창이 일어나기 어려워지는 문제점이 발생할 수 있다.On the other hand, if the cured intermediate layer from the UV-curable resin composition for the donor film has a storage modulus of less than about 3.5 GPa, organic transfer may occur to areas that should not be patterned when performing laser thermal transfer, thereby causing a problem of lowering patterning reliability. If the storage modulus exceeds about 5.5 GPa, thermal expansion by the laser in the intermediate layer may be difficult to occur during laser thermal transfer.
상기 도너 필름용 광경화형 수지 조성물은, 구체적으로, 우레탄 아크릴레이트계, 에폭시 아크릴레이트계, 에스테르 아크릴레이트계, 카도계(cardo-based) 아크릴레이트계 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나의 아크릴레이트계 모노머, 아크릴레이트계 올리고머, 아크릴레이트계 프리폴리머 또는 이들의 조합을 포함하는 광경화성 화합물과, 여기에 가교성 아크릴레이트계 모노머, 광개시제 등의 첨가제를 더 포함할 수 있다.The photocurable resin composition for a donor film is specifically, at least one selected from the group consisting of urethane acrylates, epoxy acrylates, ester acrylates, cardo-based acrylates, and combinations thereof. A photocurable compound including an acrylate monomer, an acrylate oligomer, an acrylate prepolymer, or a combination thereof may further include additives such as a crosslinkable acrylate monomer and a photoinitiator.
상기 광경화성 화합물의 상기 아크릴레이트 올리고머는 중량평균분자량 약 500 내지 약 20000 일 수 있다.The acrylate oligomer of the photocurable compound may have a weight average molecular weight of about 500 to about 20000.
예를 들어, 상기 도너 필름용 광경화형 수지 조성물은 상기 광경화성 화합물로서 전술한 아크릴레이트계 올리고머를 약 20 내지 약 60 중량% 포함할 수 있다.For example, the photocurable resin composition for a donor film may include about 20 to about 60 wt% of the aforementioned acrylate oligomer as the photocurable compound.
상기 우레탄아크릴레이트는 우레탄 화합물에 아크릴레이트기를 부여하여 UV 경화될 수 있게 한 것으로서, 우레탄 결합과 아크릴레이트기를 갖는 화합물의 총칭이다. 우레탄 결합은 이소시아네이트계 모노머와 폴리올이 중합반응하여 형성될 수 있고, 예를 들어, 상기 우레탄 아크릴레이트계 광경화성 올리고머는 이소시아네이트계 화합물이 (메타)아크릴산히드록시알킬에스테르계 화합물과 반응하여 형성된 우레탄 결합을 포함하고, 중량평균분자량 약 500 내지 약 20000 정도로 중합되어 형성된 올리고머일 수 있다.The urethane acrylate is to give an acrylate group to the urethane compound to be UV cured, it is a generic name of a compound having a urethane bond and an acrylate group. The urethane bond may be formed by polymerizing an isocyanate monomer and a polyol. For example, the urethane acrylate photocurable oligomer may be a urethane bond formed by reacting an isocyanate compound with a (meth) acrylic acid hydroxyalkyl ester compound. It may include an oligomer formed by polymerizing a weight average molecular weight of about 500 to about 20000.
상기 이소시아네이트계 화합물의 구체적인 예로는 헥사메틸렌 디이소시아네이트 (Hexamethylene diisocyanate, HMDI), 이소포론 디이소시아네이트 (Isophorone diisocyanate, IPDI)와 같은 지방족 이소시아네이트계 화합물 또는 톨루엔 디이소시아네이트 (Toluene diisocyanate, TDI), 메틸렌 다이페닐 디이소시아네이트 (methylene diphenyl diisocyanate, MDI)와 같은 방향족 이소시아네이트계 화합물 등을 들 수 있고, 이들을 단독 또는 2종 이상 혼합하여 사용할 수 있다.Specific examples of the isocyanate compounds include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), or toluene diisocyanate (TDI), and methylene diphenyl diisocyanate. Aromatic isocyanate compounds, such as isocyanate (methylene diphenyl diisocyanate, MDI), etc. are mentioned, These can be used individually or in mixture of 2 or more types.
상기 (메타)아크릴산히드록시알킬에스테르계 화합물의 구체적인 예로는 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-히드록시헥실 (메타)아크릴레이트, 8-히드록시옥틸 (메타)아크릴레이트, 2-히드록시에틸렌글리콜 (메타)아크릴레이트 또는 2-히드록시프로필렌글리콜 (메타)아크릴레이트 등일 수 있고, 이들의 조합이 사용될 수 있다. Specific examples of the (meth) acrylic acid hydroxyalkyl ester compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and the like, and combinations thereof This can be used.
상기 에폭시 아크릴레이트는 광경화형 화합물로서 에폭시기 함유 에폭시기 화합물에 아크릴레이트기가 부여된 화합물로서, 구체적인 예를 들면, 비스페놀 A 디글리시딜에테르, 수소 첨가 비스페놀 A 디글리시딜에테르 또는 페놀 노볼락 에폭시 수지의 (메트)아크릴산 부가물인 에폭시아크릴레이트계 화합물 등을 들 수 있다.The epoxy acrylate is a compound in which an acrylate group is given to an epoxy group-containing epoxy group compound as a photocurable compound, and specific examples thereof include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or a phenol novolak epoxy resin. Epoxy acrylate type compounds etc. which are the (meth) acrylic acid addition products of these are mentioned.
상기 에스테르 아크릴레이트는 광경화형 화합물로서 에스테르 화합물에 아크릴레이트기가 부여된 화합물로서, 구체적인 예를 들면, 트리메틸올프로판트리아크릴레이트, 펜타에리트리톨테트라아크릴레이트 또는 디펜타에리트리톨헥사아크릴레이트 등의 다가 알코올의 다관능 폴리에스테르아크릴레이트계 화합물일 수 있다.The ester acrylate is a compound in which an acrylate group is added to an ester compound as a photocurable compound, and specific examples thereof include polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate. It may be a polyfunctional polyester acrylate compound.
상기 카도계 아크릴레이트 (또는 플루오렌계 아크릴레이트)는 광경화형 화합물로서, 구체적으로, 하기 화학식 1의 카도계 화합물과 디안하이드라이드 화합물, 디올 화합물, 디아크릴산 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 반응시켜 광경화 가능한 아크릴레이트가 부여된 화합물일 수 있다.The cardo-based acrylate (or fluorene-based acrylate) is a photocurable compound, specifically, at least one selected from the group consisting of a cardo-based compound of Formula 1, a dianhydride compound, a diol compound, diacrylic acid, and a combination thereof It may be a compound endowed with a photocurable acrylate by reacting one.
[화학식 1][Formula 1]
Figure PCTKR2014007159-appb-I000002
Figure PCTKR2014007159-appb-I000002
상기 식에서, Where
R1 및 R2는, 각각 독립적으로, -OH, -NH2, -O-CH2-CH2-OH 또는 -COOH이다.R 1 and R 2 are each independently —OH, —NH 2 , —O—CH 2 —CH 2 —OH, or —COOH.
상기 도너 필름용 광경화형 조성물은 상기 광경화성 화합물 약 30 내지 약 70 중량% 포함할 수 있다.The photocurable composition for a donor film may include about 30 to about 70% by weight of the photocurable compound.
상기 가교성 아크릴레이트 모노머는 광경화 가능한 다양한 모노머가 사용가능하고, 예를 들어, 2개 내지 4개의 아크릴레이트 관능기 함유 모노머일 있다. 상기 가교성 아크릴레이트 모노머의 구체적인 예를 들면, 1,2-에틸렌글리콜 디아크릴레이트, 1,12-도데탄디올 아크릴레이트, 1,4-부탄디올 디(메타)아크릴레이트, 1,6-헥산디올 디(메타)아크릴레이트, 네오펜틸글리콜 디(메타)아크릴레이트, 폴리에틸렌글리콜 디(메타)아크릴레이트, 네오펜틸글리콜아디페이트(neopentylglycol adipate) 디(메타)아크릴레이트, 히드록시피발산(hydroxyl puivalic acid) 네오펜틸글리콜 디(메타)아크릴레이트, 디시클로펜타닐(dicyclopentanyl) 디(메타)아크릴레이트, 카프로락톤 변성 디시클로펜테닐 디(메타)아크릴레이트, 에틸렌옥시드 변성 디(메타)아크릴레이트, 디(메타)아크릴록시 에틸 이소시아누레이트, 알릴(allyl)화 시클로헥실 디(메타)아크릴레이트, 트리시클로데칸디메탄올(메타)아크릴레이트, 디메틸롤 디시클로펜탄 디(메타)아크릴레이트, 에틸렌옥시드 변성 헥사히드로프탈산 디(메타)아크릴레이트, 트리시클로데칸 디메탄올(메타)아크릴레이트, 네오펜틸글리콜 변성 트리메틸프로판 디(메타)아크릴레이트, 아다만탄(adamantane) 디(메타)아크릴레이트 또는 9,9-비스[4-(2-아크릴로일옥시에톡시)페닐]플루오렌(fluorine) 등의 2관능형 아크릴레이트; 트리메틸롤프로판 트리(메타)아크릴레이트, 디펜타에리쓰리톨 트리(메타)아크릴레이트, 프로피온산 변성 디펜타에리쓰리톨 트리(메타)아크릴레이트, 펜타에리쓰리톨 트리(메타)아크릴레이트, 프로필렌옥시드 변성 트리메틸롤프로판 트리(메타)아크릴레이트, 3 관능형 우레탄 (메타)아크릴레이트 또는 트리스(메타)아크릴록시에틸이소시아누레이트 등의 3관능형 아크릴레이트; 디글리세린 테트라(메타)아크릴레이트 또는 펜타에리쓰리톨 테트라(메타)아크릴레이트 등의 4관능형 아크릴레이트; 프로피온산 변성 디펜타에리쓰리톨 펜타(메타)아크릴레이트 등의 5관능형 아크릴레이트; 및 디펜타에리쓰리톨 헥사(메타)아크릴레이트, 카프로락톤 변성 디펜타에리쓰리톨 헥사(메타)아크릴레이트 또는 우레탄 (메타)아크릴레이트 (ex. 이소시아네이트 단량체 및 트리메틸롤프로판 트리(메타)아크릴레이트의 반응물 등의 6관능형 아크릴레이트 등을 들 수 있으나, 이에 제한되는 것은 아니다.As the crosslinkable acrylate monomer, various photocurable monomers may be used, for example, 2 to 4 acrylate functional group-containing monomers. Specific examples of the crosslinkable acrylate monomer include 1,2-ethylene glycol diacrylate, 1,12-dodecanediol acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid ) Neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (Meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) arc Ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) Bifunctional acrylates such as acrylate or 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional acrylates, such as propionic acid modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate And 6 functional acrylates such as reactants, but are not limited thereto.
상기 도너 필름용 광경화형 수지 조성물은 상기 가교성 아크릴레이트 모노머를 약 20 내지 약 60 중량% 포함할 수 있다.The photocurable resin composition for a donor film may include about 20 to about 60 wt% of the crosslinkable acrylate monomer.
상기 광개시제의 예로는 벤조인메틸에테르, 2,4,6-트리메틸벤조일 디페닐포스핀옥사이드, 비스(2,4,6-트리메틸벤조일) 페닐포스핀옥사이드, α,α-메톡시-α-하이드록시아세토페논, 2-벤조일-2-(디메틸아미노)-1-[4-(4-몰포닐) 페닐]-1-부타논, 2,2-디메톡시-2-페닐아세토페논, 옥심에스터계 등으로 이루어진 군으로부터 선택된 하나 이상을 들 수 있다. 상기 도너 필름용 UV경화형 수지 조성물은 상기 광개시제를 약 0.1 내지 약 10 중량%로 포함할 수 있다. Examples of the photoinitiator include benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, α, α-methoxy-α-hydro Roxacytophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, oxime ester system And one or more selected from the group consisting of. The UV curable resin composition for a donor film may include about 0.1 to about 10% by weight of the photoinitiator.
상기 도너 필름용 광경화형수지 조성물의 경화물이 전술한 범위의 유리전이온도 및 상온에서의 저장 모듈러스를 갖도록 구현하기 위해, 예시적으로 하나의 방법을 제시하면, 상기 광경화형 화합물로서 준비하는 올리고머 원재료의 유리전이온도를 약 -50℃ 에서 약 60℃ 범위로 제한하고, 광개시제를 통해 경화된 고분자 네트워크 구조를 형성한 후 경화물의 유리전이 온도가 약 40℃ 내지 약 180℃가 되도록 제조할 수 있다. In order to implement the cured product of the photocurable resin composition for a donor film to have a storage modulus at the glass transition temperature and room temperature in the above-described range, by way of example, an oligomeric raw material prepared as the photocurable compound The glass transition temperature of the range of about -50 ℃ to about 60 ℃, and after forming a cured polymer network structure through a photoinitiator can be prepared so that the glass transition temperature of the cured product is about 40 ℃ to about 180 ℃.
상기 올리고머 원재료의 유리전이온도를 제한하기 위해, 예를 들어, 우레탄 아크릴레이트 올리고머의 경우 이소시아네이트와 (메타)아크릴산히드록시알킬에스테르가 방향족기를 포함하도록 하여 경질(hard)의 반복단위를 갖게 함으로써 경화물의 유리전이온도를 올릴 수 있다. In order to limit the glass transition temperature of the oligomer raw material, for example, in the case of urethane acrylate oligomer, isocyanate and (meth) acrylic acid hydroxyalkyl ester include an aromatic group to give a hard repeating unit The glass transition temperature can be raised.
또한, 상기 도너 필름용 광경화형 수지 조성물은 전술한 수치 범위의 저장 모듈러스를 구현하기 위하여, 상기 광경화성 화합물의 반복 단위(repeat unit)를 구성하는 모노머의 종류, 분자량, 함량 등을 변경하여 조절할 수 있다. 예를 들어, 반복 단위가 경질(hard) 유형인 방향족으로 구성되면 상기 저장 모듈러스가 증가하게 된다. 한편, 분자량을 통해서도 저장 모듈러스를 조절할 수 있는데, 분자량이 큰 경우 경화 지점(site) 간의 간격이 길어져 가교 밀도(crosslinking density)가 낮아지게 되고 이로 인해 저장 모듈러스가 감소하는 결과를 나타낸다. 또한, 지방족기 함유 모노머와 방향족기 함유 모노머의 함량을 조절하고, 분자량이 큰 구성요소와 작은 구성 요소의 함량을 조절하여 상기 도너 필름용 광경화형 수지 조성물의 경화물이 전술한 범위 내의 저장 모듈러스를 구현할 수 있다.In addition, the photocurable resin composition for a donor film can be adjusted by changing the type, molecular weight, content, etc. of the monomer constituting a repeat unit of the photocurable compound in order to implement the storage modulus of the above-described numerical range have. For example, the storage modulus increases if the repeating unit consists of an aromatic of hard type. On the other hand, it is also possible to control the storage modulus through the molecular weight, when the molecular weight is large, the interval between the curing sites (site) is long and the crosslinking density (crosslinking density) is lowered, which results in a decrease in the storage modulus. In addition, by adjusting the content of the aliphatic group-containing monomer and the aromatic group-containing monomer, by adjusting the content of the high molecular weight component and the small component component of the photocurable resin composition for the donor film storage modulus within the above-mentioned range Can be implemented.
일 구현예에서, 상기 도너 필름용 광경화형 수지 조성물은 중량평균분자량 약 500 내지 약 20000인 올리고머와 모노머의 함량비가 약 1:4 내지 약 4:1이 되도록 포함할 수 있고, 구체적으로 상기 모노머는 지방족기 함유 모노머일 수 있고, 상기 올리고머는 방향족기 함유 올리고머일 수 있다.In one embodiment, the photocurable resin composition for a donor film may include a content ratio of oligomer and monomer having a weight average molecular weight of about 500 to about 20000 to about 1: 4 to about 4: 1, specifically, the monomer It may be an aliphatic group-containing monomer, the oligomer may be an aromatic group-containing oligomer.
다른 구현예에서, 지방족기 모노머와 방향족기 모노머를 동시에 포함되게 하지 않을 수 있다.In another embodiment, the aliphatic monomer and the aromatic monomer may not be included at the same time.
또한, 상기 도너 필름용 광경화성 수지 조성물은 발명의 효과에 영향을 미치지 않는 범위에서, 가교제, 자외선 안정제, 산화 방지제, 조색제, 보강제, 충진제, 소포제, 계면 활성제, 가소제 및 이들의 조합으로 이루어진 군으로부터 선택된 하나 이상의 첨가제를 더 포함할 수 있다. In addition, the photocurable resin composition for a donor film is from the group consisting of a crosslinking agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, a plasticizer, and combinations thereof in a range that does not affect the effect of the invention. It may further comprise one or more additives selected.
본 발명의 다른 구현예에서, 기재층, 광열변환층, 중간층 및 전사층을 포함하는 도너 필름을 제공한다. 상기 중간층은 전술한 도너 필름용 광경화성 수지 조성물을 경화시켜 제조된다.In another embodiment of the present invention, a donor film including a substrate layer, a photothermal conversion layer, an intermediate layer, and a transfer layer is provided. The said intermediate | middle layer is manufactured by hardening | curing the photocurable resin composition for donor films mentioned above.
상기 도너 필름은 레이저 열전사를 이용한 패터닝시 전사층의 유기물이 전사되는 성능을 개선시킬 수 있다.The donor film may improve the performance of transferring the organic material of the transfer layer during patterning using laser thermal transfer.
패터닝은 전사품질을 결정하는 요소 중의 하나로 전술한 도너 필름용 광경화형 수지 조성물로부터 형성된 중간층의 저장 모듈러스를 조절하여 열팽창이 잘 일어나도록 하며, 유리전이온도를 조절하여 열팽창 온도에서 중간층의 변형 및 부풀어오름을 최적화 하고자 한다. Patterning is one of the factors that determine the transfer quality, so that thermal expansion occurs well by adjusting the storage modulus of the intermediate layer formed from the photocurable resin composition for a donor film described above, and controlling the glass transition temperature to deform and swell the intermediate layer at the thermal expansion temperature. We want to optimize
상기 도너 필름은 유기발광표시장치 등의 디스플레이 소자의 제조에 유용하게 사용될 수 있다.The donor film may be usefully used for manufacturing a display device such as an organic light emitting display device.
도 1은 도너 필름(10)의 단면도이다. 도 1에서, 상기 도너 필름(10)은 기재층(11), 상기 기재층(11)의 상부에 형성된 광열변환층(12) 및 상기 광열변환층(12) 상부에 형성된 중간층(13)을 포함한다. 1 is a cross-sectional view of the donor film 10. In FIG. 1, the donor film 10 includes a base layer 11, a photothermal conversion layer 12 formed on the base layer 11, and an intermediate layer 13 formed on the photothermal conversion layer 12. do.
도 1에서 나타나듯이, 상기 중간층(13) 상부에 형성된 전사층(14)이 형성될 수 있다.As shown in FIG. 1, a transfer layer 14 formed on the intermediate layer 13 may be formed.
상기 기재필름(11)은 유리; 또는 폴리에스테르, 폴리카보네이트, 폴리올레핀, 폴리비닐 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 투명 필름일 수 있다. The base film 11 is glass; Or a transparent film including at least one selected from the group consisting of polyester, polycarbonate, polyolefin, polyvinyl, and combinations thereof.
상기 기재필름(11)은, 구체적으로, 폴리에틸렌 테레프탈레이트(PET; Polyethylene terephthalate) 필름 또는 폴리에틸렌 나프탈레이트(PEN; Polyethylene naphthalate) 필름이고, 상기 재질의 기재필름은 가공성, 열안정성 및 투명성 측면에서 가장 바람직하다. The base film 11 is specifically, a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film, and the base film of the material is most preferable in view of processability, thermal stability and transparency. Do.
또한, 상기 기재필름(11)의 표면은 당업자에게 알려진 표면처리, 예를 들어 코로나, 플라즈마 등의 표면처리로 개질하여 후속 공정으로 광열변환층(12) 적층시 부착성, 표면장력 등을 조절하는 것도 가능하다.In addition, the surface of the base film 11 is modified by a surface treatment known to those skilled in the art, for example, a surface treatment such as corona, plasma, and the like to control adhesion, surface tension, etc. when the photothermal conversion layer 12 is laminated in a subsequent process. It is also possible.
상기 도너 필름(10)은 상기 기재필름(11)에 형성되는 프라이머층(미도시)을 추가로 포함할 수 있다. 예를 들어, 상기 기재필름(11) 및 광열변환층(12) 사이에 프라이머층이 형성될 수 있다.The donor film 10 may further include a primer layer (not shown) formed on the base film 11. For example, a primer layer may be formed between the base film 11 and the photothermal conversion layer 12.
상기 프라이머층은 기재필름과 인접한 층 사이의 온도 전달을 제어하고, 기재필름(11)과 인접한 층과의 접착성을 향상시키고, 광열변환층(12)으로의 이미지 형성 방사선 전달을 제어하기 위한 것으로, 프라이머층을 형성하지 않는 경우 레이저를 이용한 전사공정에서 기재필름(11)과 광열변환층(12)이 분리되는 현상이 발생할 수 있다.The primer layer is to control the temperature transfer between the base film and the adjacent layer, to improve the adhesion between the base film 11 and the adjacent layer, and to control the image forming radiation transfer to the photothermal conversion layer 12. If the primer layer is not formed, a phenomenon in which the base film 11 and the photothermal conversion layer 12 are separated in a transfer process using a laser may occur.
이러한 프라이머층에 적합한 소재로는 아크릴계 수지, 폴리우레탄계 수지, 폴리에스테르계 수지 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 사용할 수 있다. As a suitable material for such a primer layer, at least one selected from the group consisting of acrylic resins, polyurethane resins, polyester resins, and combinations thereof may be used.
상기 프라이머층과 기재필름(11) 간 또는 프라이머층과 광열변환층(12) 간 내열밀착력이 불량하면 레이저를 이용한 전사공정에서 기재필름(11)과 광열변환층(12)이 분리될 수 있다.If the heat-resistant adhesion between the primer layer and the base film 11 or between the primer layer and the photothermal conversion layer 12 is poor, the base film 11 and the photothermal conversion layer 12 may be separated in a transfer process using a laser.
상기 광열변환층(12)은 적외선-가시광선 영역의 빛을 흡수하여 상기 빛의 일부를 열로 변환시키는 층으로, 열경화성수지를 포함하는 수지 조성물과 광열 변환물질로 이루어진다.The photothermal conversion layer 12 is a layer that absorbs light in the infrared-visible ray region and converts a part of the light into heat, and is made of a resin composition including a thermosetting resin and a photothermal conversion material.
상기 중간층(13)은 전술한 도너 필름용 광경화성 수지 조성물을 코팅하여 열경화 또는 광경화하여 형성될 수 있고, 상기 중간층(13)은 광열변환층(12)에서 발생하는 열에 의해 전사층이 전사될 때, 광열 변환층(12) 내부에 존재하는 광열 변환물질이 함께 전사되는 것을 방지하기 위하여, 그리고 광열변환층(12)에서 발생한 열이 전사층에 전달되어 열에 의해 타버리는 것을 방지할 수 있다. 이와 함께, 상기 중간층(13)은 전술한 바와 같이 패터닝 신뢰성이 우수하다.The intermediate layer 13 may be formed by coating the above-mentioned photocurable resin composition for a donor film and thermosetting or photocuring, wherein the intermediate layer 13 is transferred by a heat generated in the photothermal conversion layer 12. In this case, in order to prevent the photothermal conversion material present in the photothermal conversion layer 12 from being transferred together, and heat generated in the photothermal conversion layer 12 may be transferred to the transfer layer and burned out by the heat. . In addition, the intermediate layer 13 is excellent in patterning reliability as described above.
상기 중간층(13)은 낮은 표면 에너지를 갖는 것이 바람직하다. 상기 중간층(13)이 낮은 표면에너지를 가짐으로써 작은 열팽창에도 유기물 전사가 용이한 장점이 있다.The intermediate layer 13 preferably has a low surface energy. Since the intermediate layer 13 has a low surface energy, there is an advantage in that the organic material is easily transferred even in a small thermal expansion.
구체적으로, 상기 중간층(13)은 표면에너지가 약 11 mN/m 내지 약 21 mN/m 일 수 있다.Specifically, the intermediate layer 13 may have a surface energy of about 11 mN / m to about 21 mN / m.
상기 중간층(13)은 예를 들어 약 1 ㎛ 내지 약 5 ㎛의 두께로 형성될 수 있다. 상기 중간층(13)의 두께가 약 1 ㎛ 미만일 때는 광열변환층에서 발생한 열로 인해 전사층의 유기물이 손상을 입을 수 있고, 약 5 ㎛ 초과하면 충분히 부풀어 오르지 않아 전사 성능이 안 좋아질 수 있다.The intermediate layer 13 may be formed to have a thickness of, for example, about 1 μm to about 5 μm. When the thickness of the intermediate layer 13 is less than about 1 μm, the organic material of the transfer layer may be damaged due to the heat generated in the photothermal conversion layer. If the thickness of the intermediate layer 13 is greater than about 5 μm, the transfer performance may not be sufficiently swelled.
상기 전사층(14)은 전형적으로 리셉터로 전사하기 위한 하나 이상의 층을 포함한다. 예를 들어, 전계발광재료 또는 전기적으로 활성인 재료를 포함하는 유기, 무기, 유기금속성 및 다른 재료를 사용하여 형성될 수 있다. 구체적으로, 폴리(페닐렌비닐렌), 폴리-파라-페닐렌, 폴리플루오렌, 폴리디알킬플루오렌, 폴리티오펜, 폴리(9-비닐카바졸), 폴리(N-비닐카바졸-비닐알콜) 공중합체, 트리아릴아민, 폴리노르보넨, 폴리아닐린, 폴리아릴폴리아민, 트리페닐아민-폴리에테르케톤 등이 사용될 수 있다.The transfer layer 14 typically includes one or more layers for transferring to the receptor. For example, it may be formed using organic, inorganic, organometallic and other materials, including electroluminescent materials or electrically active materials. Specifically, poly (phenylenevinylene), poly-para-phenylene, polyfluorene, polydialkylfluorene, polythiophene, poly (9-vinylcarbazole), poly (N-vinylcarbazole-vinyl Alcohol) copolymers, triarylamine, polynorbornene, polyaniline, polyarylpolyamine, triphenylamine-polyetherketone and the like can be used.
또한, 상기 전사층(14)은 제조하고자 하는 유기발광소자의 특성에 합치되도록 공지의 발광물질, 홀 전달성 유기물질, 전자 전달성 유기물질 중에서 선택되는 1 이상의 물질을 더 포함할 수 있으며, 추가적으로 비발광 저분자 물질, 비발광 전하전달 고분자 물질 및 경화 가능 유기반인더 물질 중 적어도 하나를 포함하는 화합물을 포함할 수 있다.In addition, the transfer layer 14 may further include one or more materials selected from known light emitting materials, hole transporting organic materials, and electron transporting organic materials so as to match the characteristics of the organic light emitting device to be manufactured. It may include a compound comprising at least one of a non-luminescent low molecular material, a non-luminescent charge transfer polymer material and a curable organic semi-inder material.
이하, 본 발명의 실시예 및 비교예를 기재한다. 그러한 하기한 실시예는 본 발명의 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, the Example and comparative example of this invention are described. Such following examples are only examples of the present invention, and the present invention is not limited to the following examples.
(실시예)(Example)
실시예 1Example 1
방향족기를 갖는 카도계 아크릴레이트의 광경화성 화합물 (중량평균분자량 3000) 50 wt%, 지방족기를 가진 2관능 아크릴레이트 모노머 45 wt%, 광개시제 5 wt%를 혼합하여 광경화성 수지 조성물을 준비하였다.A photocurable resin composition was prepared by mixing 50 wt% of a photocurable compound (weight average molecular weight 3000) of a cardo-based acrylate having an aromatic group, 45 wt% of a bifunctional acrylate monomer having an aliphatic group, and 5 wt% of a photoinitiator.
상기 광경화성 수지 조성물에 대하여 유리전이온도를 측정한 결과 80℃이었다.It was 80 degreeC when the glass transition temperature was measured about the said photocurable resin composition.
폴리에스테르 필름의 기재층 상에 카본블랙의 광열변환물질을 포함하는 광열변환층을 3㎛ 두께로 형성하고, 그 상부에 상기 준비한 우레탄아크릴레이트계 수지 조성물을 3㎛ 두께로 코팅한 후, UV 램프를 이용하여 자외선을 조사하여 경화시킴으로써 중간층을 제조하여 도너 필름을 제조하였다. After forming a photothermal conversion layer containing a carbon black photothermal conversion material on the substrate layer of the polyester film to a thickness of 3㎛, and coating the urethane acrylate-based resin composition prepared above to a thickness of 3㎛, UV lamp The donor film was manufactured by preparing an intermediate layer by irradiating with UV and curing.
상기 카도계 아크릴레이트는 방향족의 5원환과 6원환이 교차된 경질 구조를 갖는 경질 타입 올리고머 (분자량 3000)이고, 상기 2관능 모노머를 상기 함량비로 배합한 조성물이 원하는 범위 내의 저장 모듈러스를 구현할 수 있다. 상기 제조된 중간층에 대하여 유리전이온도 및 저장 모듈러스를 측정하였다.The cardo-based acrylate is a hard type oligomer (molecular weight 3000) having a hard structure in which an aromatic 5-membered ring and a 6-membered ring cross each other, and the composition combining the bifunctional monomer in the content ratio may realize a storage modulus within a desired range. . The glass transition temperature and storage modulus of the prepared intermediate layer were measured.
실시예 2Example 2
광경화성 수지 조성물을 방향족 구성물을 갖는 우레탄 아크릴레이트 (중량평균분자량 5000) 60 wt%, 2관능 아크릴레이트 모노머 35 wt% 및 광개시제 5 wt%를 포함하도록 제조한 점을 제외하고 실시예 1에서와 동일한 방법으로 도너 필름을 제조하였다. Same as in Example 1 except that the photocurable resin composition was prepared to contain 60 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 35 wt% of the bifunctional acrylate monomer, and 5 wt% of the photoinitiator. A donor film was produced by the method.
실시예 3Example 3
광경화성 수지 조성물을 방향족 구성물을 갖는 우레탄 아크릴레이트 (중량평균분자량 6000) 75 wt%, 2관능 아크릴레이트 모노머 20 wt% 및 광개시제 5 wt%를 포함하도록 제조한 점을 제외하고 실시예 1에서와 동일한 방법으로 도너 필름을 제조하였다.The photocurable resin composition was the same as in Example 1 except that the photocurable resin composition was prepared to contain 75 wt% of urethane acrylate (weight average molecular weight 6000) having an aromatic constituent, 20 wt% of a bifunctional acrylate monomer, and 5 wt% of a photoinitiator. A donor film was produced by the method.
비교예 1Comparative Example 1
광경화성 수지 조성물을 방향족 구성물을 갖는 우레탄 아크릴레이트 (중량평균분자량 5000) 80 wt%, 2관능 아크릴레이트 모노머 15 wt% 광개시제 5 wt%를 포함하도록 제조한 점을 제외하고 실시예 1에서와 동일한 방법으로 도너 필름을 제조하였다. The same method as in Example 1, except that the photocurable resin composition was prepared to contain 80 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 15 wt% of bifunctional acrylate monomer, and 5 wt% of a photoinitiator. The donor film was prepared by the following.
비교예 2Comparative Example 2
광경화성 수지 조성물을 방향족 구성물을 갖는 우레탄 아크릴레이트 (중량평균분자량 5000) 30 wt%, 2관능 아크릴레이트 모노머 65 wt% 광개시제 5 wt%를 포함하도록 제조한 점을 제외하고 실시예 1에서와 동일한 방법으로 도너 필름을 제조하였다. The same method as in Example 1 except that the photocurable resin composition was prepared to contain 30 wt% of urethane acrylate (weight average molecular weight 5000) having an aromatic constituent, 65 wt% of bifunctional acrylate monomer, and 5 wt% of a photoinitiator. The donor film was prepared by the following.
비교예 3Comparative Example 3
광경화성 수지 조성물을 지방족 구성물을 갖는 에폭시 아크릴레이트 (중량평균분자량 3000) 50 wt%, 3관능 아크릴레이트 모노머 45 wt% 광개시제 5 wt%를 포함하도록 제조한 점을 제외하고 실시예 1에서와 동일한 방법으로 도너 필름을 제조하였다.The same method as in Example 1, except that the photocurable resin composition was prepared to contain 50 wt% of epoxy acrylate (weight average molecular weight 3000) having an aliphatic constituent, 45 wt% of trifunctional acrylate monomer, and 5 wt% of a photoinitiator. The donor film was prepared by the following.
평가evaluation
실시예 1-2 및 비교예 1-2의 도너 필름의 중간층에 대하여 유리전이온도와 저장 모듈러스와 유리전이온도의 평가는 하기와 같이 수행하였고, 그 결과를 표 1에 기재하였다. 또한, 실시예 1-2 및 비교예 1-2의 도너 필름에 대하여 하기 방법에 따라 전사 특성을 평가하여 표 1에 평가 결과를 기재하였다.Evaluation of the glass transition temperature, storage modulus and glass transition temperature of the intermediate layer of the donor film of Example 1-2 and Comparative Example 1-2 was carried out as follows, the results are shown in Table 1. In addition, the transfer characteristics of the donor films of Example 1-2 and Comparative Example 1-2 were evaluated according to the following method, and the evaluation results are described in Table 1.
<유리전이온도 평가><Glass Transition Temperature Evaluation>
Differential scanning calorimetry (Perkin Elmer社 DSC8000): 20℃에서 200℃까지 10 ℃/min의 속도로 승온하여 측정한다. Differential scanning calorimetry (Perkin Elmer Corp. DSC8000): Measured by heating at a rate of 10 ℃ / min from 20 ℃ to 200 ℃.
<저장 모듈러스 평가>Storage Modulus Assessment
Nanoindentation: Hysitron TI750: nanoDMA mode로 상온에서 측정하여 저장 모듈러스 값을 얻었다.Nanoindentation: Hysitron TI750: Measured at room temperature in nanoDMA mode to obtain a storage modulus value.
<전사 품질 평가><Transcription quality evaluation>
하기 방법에 의해 전사 품질을 평가하였다.The transfer quality was evaluated by the following method.
1) 테스트 패턴 기판 준비: Bank 구조 두께 0.5㎛ 이하, Taper Angle 15° 이하 구조를 갖는 테스트 패턴 기판을 준비한다. Pixel 크기 11×78㎛을 갖는 테스트 패턴 기판에 유기물 DNTPD(N,N'-디페닐-N,N'-비스-[4-(페닐-m-톨일-아미노)-페닐]-비페닐-4,4'-디아민)를 100Å 두께로 증착하였다. 1) Test pattern substrate preparation: A test pattern substrate having a bank structure thickness of 0.5 μm or less and a Taper Angle of 15 ° or less is prepared. Organic DNTPD (N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4 on a test pattern substrate having a pixel size of 11 × 78 μm , 4'-diamine) was deposited to 100 mm thick.
2) 실시예 1-2 및 비교예 1-2에서 제조된 필름 면에는 TCTA((N-카바졸일)-트리페닐아민)를 500Å 두께로 증착한다.2) TCTA ((N-carbazolyl) -triphenylamine) was deposited on the film surface prepared in Example 1-2 and Comparative Example 1-2 to a thickness of 500 mm 3.
3) 테스트 패턴 기판의 DNTPD면과 실시예 1-2 및 비교예 1-2의 필름의 TCTA면을 Laser 장비 Stage에서 흡착에 의해 고정한다.3) The DNTPD surface of the test pattern substrate and the TCTA surface of the films of Examples 1-2 and Comparative Examples 1-2 are fixed by adsorption on a laser equipment stage.
4) 레이저 장비의 말단부에는 기판의 픽셀 영역과 정렬하여 이미지화할 수 있도록 마스크가 장착된다.4) At the distal end of the laser device, a mask is mounted to allow imaging with alignment with the pixel area of the substrate.
5) 준비된 시료의 기재(PET면)으로 레이저 빔을 1.5J/㎠ 의 에너지 량으로 조사하여 스캐닝한다. 5) The laser beam is irradiated with an amount of energy of 1.5 J / cm 2 onto the substrate (PET surface) of the prepared sample and scanned.
6) 스캐닝 이후 실시예 1-2 및 비교예 1-2에서 도너 필름을 제거 후 기판 면으로 유기물 전사 흔적을 광학 현미경을 이용하여 평가한다. 6) After scanning After removal of the donor film in Example 1-2 and Comparative Example 1-2, the organic transfer traces to the substrate surface is evaluated using an optical microscope.
표 1
구분 실시예 비교예
1 2 3 1 2 3
유리 전이 온도 [℃] 80 120 60 70 30 50
저장 모듈러스 [GPa] 3.8 4.5 3.6 6.0 2.9 3.2
전사 품질 평가 우수 우수 우수 불량 불량 불량
Table 1
division Example Comparative example
One 2 3 One 2 3
Glass transition temperature [℃] 80 120 60 70 30 50
Storage modulus [GPa] 3.8 4.5 3.6 6.0 2.9 3.2
Enterprise quality evaluation Great Great Great Bad Bad Bad
<부호의 설명><Description of the code>
10: 도너 필름10: donor film
11: 기재층11: base layer
12: 광열변환층12: photothermal conversion layer
13: 중간층13: middle layer
14: 전사층14: transfer layer

Claims (18)

  1. 조성물의 경화물의 유리전이온도가 40℃ 내지 180℃이고, 저장 모듈러스는 25℃에서 3.5 내지 5.5 GPa인The glass transition temperature of the cured product of the composition is 40 ° C to 180 ° C, and the storage modulus is 3.5 to 5.5 GPa at 25 ° C.
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  2. 제1항에 있어서,The method of claim 1,
    상기 조성물은 우레탄 아크릴레이트계, 에폭시 아크릴레이트계, 에스테르 아크릴레이트계, 카도계(cardo-based) 아크릴레이트계 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나의 아크릴레이트계 모노머, 아크릴레이트계 올리고머, 아크릴레이트계 프리폴리머 또는 이들의 조합을 포함하는 광경화성 화합물, 가교성 아크릴레이트계 모노머 및 광개시제를 포함하는The composition is at least one acrylate monomer selected from the group consisting of urethane acrylates, epoxy acrylates, ester acrylates, cardo-based acrylates, and combinations thereof, acrylate oligomers, A photocurable compound comprising an acrylate-based prepolymer or a combination thereof, a crosslinkable acrylate-based monomer and a photoinitiator
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  3. 제2항에 있어서,The method of claim 2,
    상기 우레탄아크릴레이트는 이소시아네이트계 모노머와 폴리올이 중합반응하여 형성된 것으로, 상기 이소시아네이트계 화합물은 지방족 이소시아네이트계 화합물, 방향족 이소시아네이트계 화합물 및 이들의 조합으로부터 선택된 적어도 1종 이상을 포함하고, 상기 폴리올은 (메타)아크릴산히드록시알킬에스테르계 화합물인The urethane acrylate is formed by polymerization of an isocyanate monomer and a polyol, and the isocyanate compound includes at least one or more selected from aliphatic isocyanate compounds, aromatic isocyanate compounds, and combinations thereof, and the polyol (meth) ) Acrylic acid hydroxyalkyl ester compound
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  4. 제2항에 있어서,The method of claim 2,
    상기 에폭시 아크릴레이트는 비스페놀 A 디글리시딜에테르, 수소 첨가 비스페놀 A 디글리시딜에테르, 페놀 노볼락 에폭시 수지의 (메트)아크릴산 부가물 및 이들의 조합으로부터 선택된 적어도 1종 이상을 포함하는The epoxy acrylate includes at least one or more selected from bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (meth) acrylic acid adducts of phenol novolac epoxy resins, and combinations thereof.
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  5. 제2항에 있어서,The method of claim 2,
    상기 에스테르 아크릴레이트는 다가 알코올의 다관능 폴리에스테르아크릴레이트계 화합물을 포함하는The ester acrylate includes a polyfunctional polyester acrylate compound of a polyhydric alcohol
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  6. 제2항에 있어서,The method of claim 2,
    상기 카도계 아크릴레이트는 하기 화학식 1의 카도계 화합물과 디안하이드라이드 화합물, 디올 화합물, 디아크릴산 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 반응시켜 광경화 가능한 아크릴레이트가 부여된 화합물인The cardo-based acrylate is a compound to which a photocurable acrylate is given by reacting at least one selected from the group consisting of a cardo-based compound of Formula 1, a dianhydride compound, a diol compound, diacrylic acid, and a combination thereof
    도너 필름용 광경화형 수지 조성물:Photocurable resin composition for donor film:
    [화학식 1][Formula 1]
    Figure PCTKR2014007159-appb-I000003
    Figure PCTKR2014007159-appb-I000003
    상기 식에서, Where
    R1 및 R2는, 각각 독립적으로, -OH, -NH2, -O-CH2-CH2-OH 또는 -COOH이다.R 1 and R 2 are each independently —OH, —NH 2 , —O—CH 2 —CH 2 —OH, or —COOH.
  7. 제2항에 있어서,The method of claim 2,
    상기 광경화성 화합물 30 내지 70 중량% 포함하는30 to 70 wt% of the photocurable compound
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  8. 제2항에 있어서,The method of claim 2,
    상기 가교성 아크릴레이트 모노머를 20 내지 60 중량% 포함하는20 to 60 wt% of the crosslinkable acrylate monomer
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  9. 제2항에 있어서,The method of claim 2,
    상기 가교성 아크릴레이트 모노머는 2개 내지 4개의 아크릴레이트 관능기 함유 모노머인The crosslinkable acrylate monomer is a monomer containing 2 to 4 acrylate functional groups
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  10. 제2항에 있어서,The method of claim 2,
    상기 광경화형 화합물의 유리전이온도(Tg)는 -50℃ 내지 60℃인The glass transition temperature (Tg) of the photocurable compound is -50 ℃ to 60 ℃
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  11. 제8항에 있어서,The method of claim 8,
    광개시제를 통해 경화된 고분자 네트워크 구조를 형성한 후 경화물의 유리전이 온도가 40℃ 내지 180℃가 되도록 제조된After forming the polymer network structure cured through the photoinitiator and the glass transition temperature of the cured product is prepared to be 40 ℃ to 180 ℃
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  12. 제1항에 있어서,The method of claim 1,
    중량평균분자량 500 내지 20000인 올리고머와 모노머의 함량비가 1:4 내지 4:1이 되도록 포함하는 광경화성 화합물을 포함하는Contains a photocurable compound comprising a content ratio of oligomer and monomer having a weight average molecular weight of 500 to 20000 to 1: 4 to 4: 1
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  13. 제12항에 있어서,The method of claim 12,
    상기 모노머는 지방족기 함유 모노머이고, 상기 올리고머는 방향족기 함유 올리고머인The monomer is an aliphatic group-containing monomer, the oligomer is an aromatic group-containing oligomer
    도너 필름용 광경화형 수지 조성물.Photocurable resin composition for donor films.
  14. 기재층, 광열변환층 및 중간층을 포함하고,A base layer, a photothermal conversion layer, and an intermediate layer,
    상기 중간층은 제1항 내지 제13항 중 어느 한 항에 따른 도너 필름용 광경화성 수지 조성물을 경화시켜 제조된 층인The intermediate layer is a layer prepared by curing the photocurable resin composition for a donor film according to any one of claims 1 to 13.
    도너 필름.Donor film.
  15. 제14항에 있어서,The method of claim 14,
    상기 중간층 상부에 전사층이 적층되는The transfer layer is stacked on the intermediate layer
    도너 필름.Donor film.
  16. 제14항에 있어서,The method of claim 14,
    상기 기재필름은 유리; 또는 폴리에스테르, 폴리카보네이트, 폴리올레핀, 폴리비닐 및 이들의 조합으로 이루어진 군으로부터 선택된 적어도 하나를 포함하는 투명 필름인The base film is glass; Or a transparent film comprising at least one selected from the group consisting of polyester, polycarbonate, polyolefin, polyvinyl, and combinations thereof
    도너 필름.Donor film.
  17. 제14항에 있어서,The method of claim 14,
    상기 기재필름에 형성되는 프라이머층을 추가로 포함하는Further comprising a primer layer formed on the base film
    도너 필름.Donor film.
  18. 제14항에 있어서,The method of claim 14,
    상기 중간층은 11 mN/m 내지 21 mN/m의 표면 에너지를 갖는The intermediate layer has a surface energy of 11 mN / m to 21 mN / m
    도너 필름.Donor film.
PCT/KR2014/007159 2013-09-27 2014-08-04 Photocurable resin composition for donor film and donor film WO2015046740A1 (en)

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KR1020130115417A KR101807900B1 (en) 2013-09-27 2013-09-27 Light curable resin composition for donor film and donor film
KR10-2013-0115417 2013-09-27

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KR100725023B1 (en) * 2006-10-16 2007-06-07 제일모직주식회사 Cardo type resin-containing resist composition and method for preparing a pattern by the same and a color filter using the same
KR20100020154A (en) * 2008-08-12 2010-02-22 에스에스씨피 주식회사 Radiation curable composition
KR20130072573A (en) * 2011-12-22 2013-07-02 코오롱인더스트리 주식회사 Liti donor film
KR20130078600A (en) * 2011-12-30 2013-07-10 제일모직주식회사 Thermal transfer film

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US10593908B2 (en) 2016-04-12 2020-03-17 Lg Chem, Ltd. Encapsulation film

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