CN105980161A - Thermal transfer film and organic electroluminescence element fabricated using same - Google Patents
Thermal transfer film and organic electroluminescence element fabricated using same Download PDFInfo
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- CN105980161A CN105980161A CN201480065094.9A CN201480065094A CN105980161A CN 105980161 A CN105980161 A CN 105980161A CN 201480065094 A CN201480065094 A CN 201480065094A CN 105980161 A CN105980161 A CN 105980161A
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- heat transfer
- transfer film
- carbon black
- tungsten oxide
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- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
- B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/06—Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/30—Thermal donors, e.g. thermal ribbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The present invention relates to a thermal transfer film and an organic electroluminescence element fabricated using the same, the thermal transfer film comprising: a base layer; and a light to heat conversion layer which is formed on the base layer and includes carbon black and tungsten oxide, wherein a deviation of an OD value represented by equation 1 below is approximately 4% or less: [equation 1] OD value deviation: [(|measured OD value - target OD value|)/target OD value] x 100, here, the measured OD value is an OD value respectively measured in a wavelength of 850nm and a wavelength of 1100nm.
Description
Technical field
The present invention relates to heat transfer film and the Organnic electroluminescent device using it to prepare.
Background technology
Heat transfer film has basal layer and is formed at the heat conversion layer on this basal layer.Containing such as luminescent material,
The transfer printing layer of the transfer materials of electron transport compound, hole transport compound etc. can be formed on heat conversion layer.
When heat conversion layer irradiates with laser at an absorbing wavelength, the heat that transfer printing layer can be converted by heat conversion layer
It is transferred to receptor.
Photothermal conversion (LTHC) layer comprises photothermal conversion materiat, and it absorbs the light under expectation wavelength, and makes at least
The incident illumination of a part changes into heat.
Conventional thermal transfer film has because of the absorbance difference under the wavelength of near infra red region and according to irradiation
Optical density (OD) (OD) difference depending on optical maser wavelength occurs, and the laser irradiation power during transfer process and place
Reason speed needs controlled problem.For this puts, the openest bulletin of KR patent the 2010-0028652nd
Case discloses a kind of heat transfer film, and it comprises the heat conversion layer containing carbon black.
Summary of the invention
[technical problem]
It is an object of the present invention to provide a kind of heat transfer film, its no matter optical maser wavelength and there is uniform optical density
(OD)。
It is a further object of the present invention to provide a kind of heat transfer film, it is by same procedure and without adjusting the irradiation of laser
Wavelength and additionally method and there is high thermal transfer efficiency.
[technical scheme]
Basal layer, and the heat conversion layer being formed on basal layer, this photo-thermal can be comprised according to the heat transfer film of the present invention
Conversion coating comprises carbon black and tungsten oxide, and can have the OD value deviation represented with equation 1 of 4% or less:
[equation 1]
OD value deviation=[(| measure OD value-target OD value |)/target OD value] × 100
Wherein, measuring OD value is the OD value that difference the most at a wavelength of 850 nm and is measured under 1100nm wavelength.
Basal layer, and the heat conversion layer being formed on basal layer, this photo-thermal can be comprised according to the heat transfer film of the present invention
Conversion coating comprises carbon black and tungsten oxide, and can have 0.05 or less with equation 2 represent respectively at 850nm ripple
OD value difference different (△ OD) between the long lower OD measured and the OD value measured under 1100nm wavelength:
[equation 2]
△ OD=| the OD value that the OD value measured under 850nm is measured under 1100nm |
Above-mentioned heat transfer film can be used as laser induced thermal imaging according to the Organnic electroluminescent device of the present invention
Donor membrane.
[Advantageous Effects]
The present invention provides a kind of heat transfer film, its no matter optical maser wavelength and there is uniform OD value.Additionally, the present invention can make
Heat transfer film implements the thermal transfer with identical transfer effect without adjusting laser power and processing speed, even if changing
The illumination wavelength of laser also obtains the processability of improvement.
Accompanying drawing explanation
Fig. 1 is the sectional view of the heat transfer film according to one embodiment of the present invention.
Fig. 2 is the sectional view of the heat transfer film according to another embodiment of the present invention.
Fig. 3 is the figure to wavelength of the OD value according to embodiment 2, comparative example 1 and comparative example 5.
Detailed description of the invention
[best mode]
Embodiments of the invention will be described in detail with reference to the accompanying drawings and make those skilled in the art implement easily.The present invention need to be understood
Can be implemented in various ways, and be not limited to following parties face.In the accompanying drawings, for the sake of clarity, unrelated with explanation
Part can be omitted.Description in the whole text in, same components can represent with same reference numerals.
Hereinafter, with reference to Fig. 1, the heat transfer film according to an embodiment of the invention will be described.Fig. 1 is according to the present invention
The sectional view of heat transfer film of an embodiment.
With reference to Fig. 1, basal layer 110 can be comprised according to the heat transfer film 100 of one aspect of the present invention, and be formed at basal layer 110
On heat conversion layer 115.Heat transfer film 100 can have the OD value deviation represented with equation 1 of 4% or less.
[equation 1]
OD value deviation=[(| measure OD value-target OD value |)/target OD value] Ⅹ 100
Wherein, measuring OD value is the OD value measured under the wavelength of 850nm and under the wavelength of 1100nm respectively.
In this deviation range, heat transfer film is up to uniformly transferring result, even if optical maser wavelength is in this printing transferring method
Change.Basal layer does not interferes with the OD value of heat transfer film.Furthermore, also will not in as follows and in fig. 2 described intermediate layer
Affect the OD value of heat transfer film.
In embodiment, the deviation of the OD value under the wavelength of 850nm and the OD value under the wavelength of 1100nm can be divided
It is not 0% to 4%, 0.001% to 4%, 0.001% to 3.5%, or 0.001% to 2.5%.If measuring OD value to target
The deviation of OD value is more than 4%, then heat transfer film can have the problem that luminous organic material will not be transferred.If additionally,
Measure OD value and the deviation of target OD value is more than 4%, then when laser illumination wavelength changes, due to the thermal transfer reduced
Efficiency, heat transfer film can not represent uniform OD value, and therefore, high thermal transfer efficiency can be until such as changing laser and shining
The other method of ejected wave length just can be achieved till being implemented.
As used herein, term " OD value deviation " means the OD value to measure under the wavelength of 850nm and target
The absolute value of the difference between difference between OD value or OD value and the target OD value measured under 1150nm wavelength removes
The value calculated with the percentage rate of target OD.
As used herein, term " target OD value " means that heat transfer film to be used has under each measurement wavelength
Optical density (OD) (OD) during desired optical property, and can be judged when using heat transfer film by those skilled in the art.
Additionally, the target OD value under the respective wavelength of 850nm and 1100nm can be identical.850nm's and 1100nm
Wavelength can the wavelength of laser based on the printing transferring method for luminous organic material and select.By this, no matter at OLED
The wavelength of the laser irradiated in the heat-transferring method of luminous organic material, according to the heat transfer film of embodiments of the present invention
Identical OD can be reached.Term " identical OD value " means identical OD, and the substantially phase in range of error
Same OD value.
Heat transfer film target OD value under the wavelength of 850nm and 1100nm can be respectively, such as, and 0.1 to 2.9,0.5
To 2.0, or 1.0 to 1.5.
OD under the wavelength of 850nm and 1100nm uses UV/VIS spectrogrph (Lambda1050, PERKIN
ELMER) measure.Especially, this device is for measuring the poly terephthalic acid comprising 100 μ m-thick as basal layer
The heat transfer film of second diester film and heat conversion layer (film thickness: 3 μm) OD value under each wavelength.
Additionally, heat transfer film 100 can have 0.3 or less with equation 2 represent under the wavelength of 850nm measure
OD value difference different (△ OD) between OD value and the OD value measured under the wavelength of 1100nm:
[equation 2]
△ OD=| the OD value of the measurement of OD value-under 1100nm measured under 850nm |
According to embodiments of the present invention, heat conversion layer can have 0.05 or less (such as, 0.01 to 0.05) 850
OA value difference different (△ OD) between the OD value and the OD measured under the wavelength of 1100nm that measure under nm.In this scope
In, excellent transfer efficiency and outward appearance can be obtained.
Basal layer 110 can be comprised according to the heat transfer film 100 of another embodiment of the present invention, and be formed at basal layer 110
On heat conversion layer 115, and heat transfer film 100 can have 0.05 or less with equation 2 represent at 850nm ripple
OD value difference different (△ OD) between the long lower OD value measured and the OD measured under the wavelength of 1100nm.According to this
Bright embodiment, heat conversion layer can have, such as, 0 to 0.05, or 0 to 0.01 survey under the wavelength of 850nm
OD value difference different (△ OD) between OD value and the OD value measured under the wavelength of 1100nm of amount.In this range,
Transfer efficiency and the outward appearance of excellence can be obtained.
Heat conversion layer can use the compositions for heat conversion layer to prepare.This compositions for heat conversion layer can
Comprise photothermal conversion materiat, binding agent and initiator.
Photothermal conversion materiat can comprise carbon black and tungsten oxide.Carbon black and tungsten oxide can be with 1wt% to 75wt%, 10wt%
Amount to 60wt%, 15wt% to 55wt%, or 20wt% to 30wt% is present in heat conversion layer.In this range,
The excellent heat transfer efficiency of heat conversion layer may be obtained.
According to the embodiment of the present invention, amounting to carbon black and tungsten oxide, carbon black can be deposited with the amount of 25wt% to 55wt%
, and tungsten oxide can be with the amount existence of 45wt% to 75wt%.More particularly, amount to carbon black and tungsten oxide,
Carbon black can exist with the amount of 30wt% to 50wt%, and tungsten oxide can exist with the amount of 50wt% to 70wt%.At this model
In enclosing, heat conversion layer can have the OD value measured under the wavelength of 850nm of 4% or less and at the ripple of 1100nm
The long lower OD value measured is relative to the deviation of target OD value.Carbon black and tungsten oxide in heat conversion layer each other will not
Absorption.Additionally, in this range, due to the applicable binder content compared with granule, for the group of heat conversion layer
Compound can be easily manufactured, and due to high hardening rate and non-adherent character, the heat conversion layer of preparation is used as
The heat conversion layer being suitable for.
According to the embodiment of the present invention, carbon black and tungsten oxide can be the solid phase particles with specific dimensions, and spy
Determine that there is under optical maser wavelength different absorption.1:1 can be had according to an embodiment of the invention, carbon black and tungsten oxide
To 1:2, such as, 1:1 to 1:1.2, or 1:1 to 1:1.1, the ratio of carbon black mean diameter and tungsten oxide mean diameter.
In this particle diameter ratio, because the carbon black with relatively small mean diameter can be inserted into and have relatively large mean diameter
Tungsten oxide in, it can be ensured that preparation for the uniformity of compositions of heat conversion layer and stability, and 4% or less
The deviation of measurement OD value and target OD value.
According to ASTM D2414, carbon black can have 50cc/100g to 120cc/100g, such as, 65cc/100g to 120
The oil factor (OAN) of cc/100g.Additionally, according to ASTM D3849, carbon black can have a 40nm to 200nm, such as,
The mean diameter of 58nm to 100nm.In this range, carbon black can represent effective thermal property in heat-transferring method.
With solids content, carbon black can be with 1wt% to 30wt%, such as, and 1wt% to 20wt%, 5wt% to 20wt%, or 5wt%
Amount to 10wt% is present in heat conversion layer.In this content range, may advantageously be controlled in specific wavelength
OD value.
Tungsten oxide can have 500nm or less, particularly 400nm or less, 10nm to 200nm, or 20nm
Mean diameter to 200nm.In this range, tungsten oxide can represent effective thermal property in heat-transferring method,
And OD value at a particular wavelength can be controlled by adjusting the content of tungsten oxide.According to one embodiment of the present invention
Formula, tungsten oxide can be with formula WyOzRepresent that (wherein, W is tungsten atom；O is oxygen atom；And the ratio (z/y) of z with y is
2.2 or more, or 3.0 or less.The example of tungsten oxide can comprise WO3、W18O49、W20O58、W4O11Deng.
If z/y is 2.2 or more, WO can be avoided completely2Crystallization occur mutually, and obtain photothermal conversion materiat chemical stability.
If the z/y in tungsten oxide is 3.0 or less, the free electron of q.s can be obtained, thus increase efficiency.According to this
A bright embodiment, if z/y is 2.45 or more and 3.0 or less (that is, 2.45≤z/y≤3.0), tungsten oxide can have
There is mug(unit of measure) alunite profit phase (Magneli phase), thus excellent durability is provided.According to another implementation of the invention,
Tungsten oxide can comprise the composite tungsten oxide of the element beyond containing tungsten.Composite tungsten oxide can be with formula MxWyOz
Represent (wherein, M be H, He, alkali metal, alkaline-earth metal, rare earth element, halogen, Zr, Cr, Mn, Fe,
Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、
In Sn, Pb, Sb, B, P, S, Se, Te, Ti, Nb, V, Mo, Ta, Re, Hf, Os and Bi at least one
Kind；W is tungsten atom；And O is oxygen atom).In this chemical formula, the ratio (x/y) of x with y is 0.001 or more and 1.1
Or less, and the ratio (z/y) of z with y is 2.2 or more and 3.0 or less.In this chemical formula, alkali metal can comprise Li,
Na, K, Rb, Cs or Fr.In this chemical formula, alkaline-earth metal can comprise Be, Mg, Ca, Sr, Ba or Ra.
In this chemical formula, rare earth metal can comprise Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb or Lu.In this chemical formula, halogen can comprise F, Cl, Br or I.According to the present invention
An embodiment, with formula MxWyOzThe granule of the composite tungsten oxide represented can have selected from hexagon, corner
At least one structure in shape, or cubic crystallographic structure, thus durability is provided.Such as, when composite tungsten oxide
Granule there is hexagon crystalline texture, M can be Cs, Rb, K, Ti, In, Ba, Li, Ca, Sr, Fe, and
At least one element in Sn.In one embodiment, the addition of M element, x can be determined so that x/y is
0.001 or more and 1.1 or less, such as, 0.33 ± 0.3 (0.03 to 0.63).This is because the reason of hexagon crystalline texture
Opinion x/y is 0.33.In this addition of M element, it is possible to provide heat conversion layer excellent optical.The amount of oxygen atom,
Z can be determined so that z/y is 2.2 or more and 3.0 or less.Such as, with MxWyOzThe composite tungsten oxide represented
Can be Cs0.33WO3、Rb0.33WO3、K0.33WO3、Ba0.33WO3Deng.When x, y and z fall in this range, can
The near-infrared absorbing characteristic being provided with.With the solid content meter of heat conversion layer, tungsten oxide can with 1wt% extremely
The amount of 45wt%, particularly 1wt% to 35wt%, 5wt% to 25wt%, or 5wt% to 21wt% exists.In this scope
In, the excellent heat transfer efficiency of heat conversion layer can be obtained, because heat conversion layer can be sufficiently carried out photothermal conversion.
Additionally, in this range, due to the applicable binder content compared with granule, the compositions of heat conversion layer can be made to hold
Change places manufacture, and due to its high hardening rate and non-adherent character, the heat conversion layer of preparation is used as being suitable for photo-thermal and turns
Change layer.
Binding agent can make carbon black and tungsten oxide embed the structure forming heat conversion layer.Binding agent can comprise ultraviolet can
Solidification resin, polyfunctional monomer or their mixture.UV curable resin can comprise (methyl) acrylic acid unrestrictedly
Ester resinae, phenol resin class, polyvinyl butyral resin class, polyvinyl acetate, polyvinyl acetal, poly-dichloro are sub-
Vinyl, cellulose ether, cellulose esters, NC Nitroncellulose, Merlon, poly-(methyl) alkyl acrylate esters, ring
Oxygen (methyl) esters of acrylic acid, epoxy resin, amine formate resin class, alkyd resin class, spiral shell acetal resin class,
And at least one of polybutadiene apoplexy due to endogenous wind.For the solid content meter of the compositions of heat conversion layer, ultraviolet
Curable resin can be with 10wt% to 75wt%, and the amount of particularly 15wt% to 75wt%, or 20wt% to 60wt% exists.
In this range, the substrate of stable heat conversion layer can be formed.It is specific that polyfunctional monomer can make heat conversion layer have
Hardness.More an embodiment of the invention, polyfunctional monomer can be to have one or more, and particularly two extremely
The monomer of six (methyl) acrylate groups.Especially, polyfunctional monomer can comprise multifunctional (methyl) acrylate list
At least one in multifunctional (methyl) acrylate monomer of body and fluorine richness.Multifunctional (methyl) acrylate monomer can
Comprise, such as, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, season penta
Tetrol two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two
Tetramethylolmethane five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, two (trimethylolpropane) four (methyl)
Acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, hexanediol two (methyl) acrylate, and
At least one in cyclodecane dimethanol two (methyl) acrylate.Multifunctional (methyl) acrylate of fluorine richness can lead to
Cross, such as, the fluorine richness of multifunctional (methyl) acrylate monomer and prepare.Compositions for heat conversion layer
Solid content meter, polyfunctional monomer can be with 5wt% to 70wt%, particularly 5wt% to 20wt%, or 5wt% to 20wt%
Amount exist.In this range, the substrate of applicable heat conversion layer can be formed.
For the solid meter of the compositions of heat conversion layer, binding agent can be with 35wt% to 80wt%, particularly 35wt%
Amount to 75wt% exists.In this range, the substrate of stable heat conversion layer can be formed.
In order to solidify the initiator of binding agent can be, such as, the most normally used Photoepolymerizationinitiater initiater.Example
As, initiator can comprise Alpha-hydroxy ketone, such as, 1-hydroxycyclohexylphenylketone unrestrictedly.Turn for photo-thermal
Changing the solid content meter of the compositions of layer, initiator can be with 0.1wt% to 10wt%, the amount of particularly 1wt% to 4wt%
Exist.In this range, heat conversion layer can be adequately formed, and initiator will not keep unreacted, thus avoid
OD value deteriorates.
Carbon black, tungsten oxide, binding agent and initiator can be comprised for preparing the compositions of heat conversion layer, and can enter
One step comprises dispersant.
The dispersion of carbon black core tungsten oxide and stable surfactant can be made, maybe can make the scattered polymerization of photothermal conversion materiat
Thing dispersant, such as, by being adsorbed in the steric hindrance of the dispersant on photothermal conversion materiat surface, can be used as dispersant.Example
As, perfluorinated compound can be used as dispersant.By using this perfluorinated compound can obtain the improvement of compositions
Dispersion stabilization.Perfluorinated compound can represent with chemical formula 1:
<chemical formula 1>
(CH2=CR1-C (=O)-O-)nRf
Wherein, n is the integer of 1 or bigger, R1For hydrogen or methyl, and RfFor C2To C50Fluoroalkyl, C2To C50Perfluor alkane
Base, C2To C50Fluorine stretches alkyl or C2To C50Perfluor stretches alkyl.Especially, n is the integer of 2 to 5, and RfFor C2To C15
Fluoroalkyl, C2To C15Perfluoroalkyl, C2To C15Fluorine stretches alkyl or C2To C15Perfluor stretches alkyl group.Such as, through fluorine
The compound changed can comprise 1H, 1H, 10H, 10H-perfluor-1,10-decanediol diacrylate (Exfluor unrestrictedly
Research Corporation).In terms of the carbon black amounting to 100 weight portions and tungsten oxide, perfluorinated compound can be with 1
Weight portion exists to 5 weight portions, the amount of particularly 1 weight portion to 3 weight portions.In this range, heat conversion layer can have
Have 4% or less under the wavelength of 850nm measure OD value and under the wavelength of 1100nm measurement OD value and mesh
The deviation of mark OD value, therefore, no matter optical maser wavelength, uniform OD value is all provided.
Acrylic polymer dispersant or acrylate polymer dispersant can be as polymeric dispersants.Propylene is polymerized
Thing dispersant can comprise the acrylate as main chain, such as, ethyl acrylate and butyl acrylate, or its copolymer,
And can further include for making dispersant adsorption in the functionality base of tungsten oxide granule or composite tungsten oxide particle
Group.Propylene or acrylate polymer dispersant can have the acid esters of 0mg KOH/g to 23mg KOH/g, and 30
Amine number to 50mg KOH/g.In this range, polymeric dispersant can make photothermal conversion materiat effectively disperse.Any
Applicable dispersant can be further used as dispersant.The example of the dispersant used further can comprise selected from poly-unrestrictedly
Conducting polymer in aniline, polythiophene, polypyrrole and their derivant；Selected from poly-stretching phenyl, poly-(stretching phenyl to stretch
Ethyl), polyfluorene, poly-(the dibasic thiophene of 3,4-), polyphenyl bithiophene, poly-different thiophene naphthalene, polypyrrole, poly-furan, poly-
Pyridine, poly-1,3,4-oxadiazoles, poly or poly selenophen, paracoumarone, polybenzazole, poly-pyridazine, poly-pyrene, poly-virtue
At least one semiconductive polymer in base amine and their derivant；And polyvinyl acetate and their copolymer etc..
For the solid content meter of the compositions of heat conversion layer, dispersant can be with 0.1wt% to 30wt%, particularly
0.1wt% to 10wt%, or the amount existence of 0.1wt% to 5wt%.In this range, photothermal conversion materiat may be improved
Dispersibility and thermal transfer efficiency.
Although dispersant can add with photothermal conversion materiat in the preparation of compositions dividually, but dispersant is the most permissible
The form of the dispersion liquid comprising dispersant and photothermal conversion materiat is added to compositions.Dispersion liquid can comprise, such as, and carbon
Black, tungsten oxide, dispersant and solvent.The scattered solvent not disturbing tungsten oxide or carbon black can be as applicable solvent.
To this end, solvent can comprise, such as, at least one in ketone, esters, hydro carbons and ethers.Especially, molten
Agent can comprise ketone, such as, butanone, first isobutyl ketone etc.；Esters, such as, ethyl acetate, propyl acetate, second
Isopropyl propionate, butyl acetate, isobutyl acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc.；
Hydro carbons, such as, toluene, dimethylbenzene etc.；Ethers, such as, ether, propyl ether etc..When this solvent is used, can
Improve the dispersibility of photothermal conversion materiat.
According to an embodiment of the invention, dispersion liquid can comprise the carbon black of 20wt% to 60wt%, and 24wt% is extremely
The tungsten oxide of 72wt%, the dispersant of 0.1wt% to 10wt%, and the solvent of surplus.As used herein, art
Language " surplus " means the amount of any material in dispersion liquid in addition to carbon black, tungsten oxide and dispersant.
Basal layer can be to have excellent adhesion to heat conversion layer and can control the temperature of heat conversion layer and other interlayer
The transparent resin film of transmission.Especially, basal layer can comprise TPO unrestrictedly, such as, polyester, polypropylene,
Polycyclic oxygen, polyethylene, polypropylene etc., and at least one resin molding of polystyrene apoplexy due to endogenous wind.More particularly, such as gather
The polyester film of PETP film or polyethylene naphthalate film can be as basal layer.Basal layer can have 10 μm
To 500 μm, the thickness of particularly 40 μm to 100 μm.In this range, basal layer can support heat transfer film and can
For heat transfer film.
Heat conversion layer can have 200nm or less, the surface roughness of particularly 1nm to 100nm.In this scope
In, finished product can avoid the transfer caused because of heat of compression transfer film to lose efficacy.
According to an embodiment of the invention, heat conversion layer can by make containing carbon black, tungsten oxide, binding agent,
The compositions of initiator, dispersant etc. is coated on basement membrane, and is dried this compositions and prepares.The combination of drying
Thing can be with 100mJ/cm2To 500mJ/cm2Solidification.It is dried and can carry out at 50 DEG C to 100 DEG C, particularly at 80 DEG C.
Heat conversion layer can have more than 0 μm and less than or equal to μm, particularly 0.5 μm to 5 μm, more particularly 0.5
μm is to the thickness of 3 μm.In this range, heat conversion layer can carry out thermal transfer effectively.
Hereinafter, with reference to Fig. 2, the heat transfer film according to another embodiment of the invention will be described.Fig. 2 is according to this
The sectional view of the heat transfer film of another embodiment bright.
With reference to Fig. 2, basal layer 110 can be comprised according to the heat transfer film 200 of another aspect of the present invention, be formed at basal layer 110
On heat conversion layer 115, and the intermediate layer 120 being formed on heat conversion layer 115.Except the thermal transfer shown in Fig. 2
Film contains outside intermediate layer further, and the heat transfer film that Fig. 2 shows is identical with the heat transfer film shown in Fig. 1.
Intermediate layer can as described below as minimize for the infringement of transfer materials and pollution making thermal transfer ink layer, and reduce heat
The transfer materials deformation of transfer printing layer.Additionally, intermediate layer is controlled heats transfer printing layer and the pattern district of receptor and the nothing of this receptor
The adhesion in pattern district.
According to an embodiment of the invention, it is (such as, logical that intermediate layer can comprise polymeric film, metal level, inorganic layer
Sol-gel precipitation or the steam of crossing inorganic oxide (such as, silicon dioxide, titanium oxide or other metal-oxide) sink
The layer amassed and formed) or organic/inorganic complexation layer.Thermosetting or thermoplastic can be as organic materials of organic complex layer
Material.
According to another implementation of the invention, intermediate layer can by comprising ultraviolet curing resin, polyfunctional monomer,
And the compositions of initiator is formed.Especially, intermediate layer can be the ultraviolet-curing tree comprising 40wt% to 95wt%
Fat, the polyfunctional monomer of 1wt% to 50wt%, and the cured product of the compositions of the initiator of 1wt% to 10wt%.In
Interbed can further include the fluorine compounds of ultraviolet-curing and at least the one of the silicone compounds of ultraviolet-curing
Kind.The fluorine compounds of ultraviolet-curing can comprise, such as, and multifunctional (methyl) acrylate of fluorine richness, such as,
1H, 1H, 10H, 10H-perfluor-1,10-decanediol two (methyl) acrylate.The silicone compounds of ultraviolet-curing can
Comprise unrestrictedly have (methyl) acrylic through polyether-modified diakyl-polysiloxane.
Intermediate layer can have 1 μm to 10 μm, the thickness of particularly 2 μm to 5 μm.In this range, intermediate layer can
There is the beneficial physical properties being suitable to heat transfer film.
The heat transfer film of the present invention can further include transfer printing layer.Transfer printing layer can, such as, as mentioned above as be formed at light
On the upper surface of heat conversion layer, or on the upper surface in intermediate layer.
Transfer printing layer can comprise transfer materials, and transfer materials can comprise, such as, and electroluminescent organic material etc..Work as tool
The laser having specific wavelength exposes to the transfer printing layer contacted with the surface of the receptor with specific pattern, and heat conversion layer is inhaled
Receive luminous energy and by produce thermal expansion, and the transfer materials of transfer printing layer by thermal transfer to receptor, in order to correspond to figure
Case.Transfer printing layer can comprise at least for making transfer materials be transferred to the layer of receptor.These layers can by organic and inorganic, have
Machine metal material or other material are formed, and comprise electroluminescent material or electroactive material.A reality according to the present invention
Executing mode, transfer printing layer uniformly can be coated by evaporation, splash or solvent coating.It addition, transfer printing layer can be by numeral
Printing, offset printing or splash by mask thus coat in predetermined pattern.
According to the present invention heat transfer film can unrestrictedly as the donor membrane for OLED, for laser induced thermal imaging
Donor membrane etc..
According to an embodiment of the invention, (comprise organic light-emitting diodes according to the Organnic electroluminescent device of the present invention
Pipe (OLED)) heat transfer film according to the embodiment of the present invention can be used to prepare as donor membrane.Especially, donor membrane
Can be placed on the base material forming transparent electrode layer above.As it has been described above, donor membrane can be, such as, wherein basal layer,
The film that heat conversion layer and transfer printing layer stack with this order.Then, donor membrane available energy sources is irradiated.From exposure device
The energy launched can activate heat conversion layer by basal layer, and activated heat conversion layer can be launched by thermal decomposition
Heat.Then, the heat conversion layer of donor membrane can make transfer printing layer separate with donor membrane by the thermal expansion produced so that
The luminescent layer formed by transfer materials is transferred on the base material of Organnic electroluminescent device the picture defined by pixel confining layers
On element region, reach to expect thickness with desired pattern.
Hereinafter, the present invention will be described in more detail with reference to some preferred embodiments.These embodiments of offer need to be understood only use
In illustratively illustrating, and explain as limiting the present invention never in any form.
The details of the component used in embodiment and comparative example is as follows.
(A) photothermal conversion materiat: tungsten oxide and carbon black
* tungsten oxide provides with the form of tungsten oxide particle dispersion (T-sol, AMTE Co., Ltd.).Tungsten oxide
Particle dispersion comprises the tungsten oxide granule of 30wt%, the acrylic polymer dispersant of 12wt%, and the first of 58wt%
Ethyl ketone, and tungsten oxide granule is as WO3Granule has the mean diameter of 70nm.
* carbon black is millbase (Raven 450, Columbia), and it comprises (the tool of the carbon black granules as dispersion liquid of 30wt%
It is the mean diameter of 65nm when having according to ASTM D3849 measurement, and is 65 when measuring according to ASTM D2414
The oil factor of cc/100g), the polyvinyl acetate as dispersant of 4.5wt%, and the first as solvent of 65.5wt%
Ethyl ketone.
(B) binding agent: as plexiglass and the epoxy acrylate tree of ultraviolet curing resin
Fat, and the trifunctional's acrylate monomer (SR351 of Sartomer) as polyfunctional monomer
(C) initiator: Irgacure 184 (CIBA)
(D) basal layer: polyethylene terephthalate film (A4100 of PET, Toyobo, thickness: 75 μm)
Embodiment 1
To the butanone as solvent of 100 weight portions, add the polymethyl methacrylate of 25 weight portions, 30 weight portions
Epocryl, trifunctional's acrylate monomer of 8 weight, and the initiator of 2 weight portions.Then,
Blend compositions.To the mixture obtained, add carbon black dispersion and the mixing of tungsten oxide dispersion liquid of 60 weight portions
Thing (carbon black dispersion of 50wt%:50wt% and the ratio of tungsten oxide dispersion liquid).Then, mixture is stirred 30
Minute.For tungsten oxide and the dispersion stabilization of carbon black, add the perfluorinated compound (Exfluor of 0.5 weight portion
The 1H of Research Corporation, 1H, 10H, 10H-perfluor-1,10-decyl diacrylate) prepare for photothermal conversion
The compositions of layer.Prepare and be just used for compositions No. 8 bars of use of heat conversion layer and rod is applied to PET film, use device
Tool is dried 2 minutes at 80 DEG C, and under ultraviolet light with 300mJ/cm2Solidification, it is thus achieved that comprise basal layer and photothermal conversion
The heat transfer film (film thickness: 3 μm) of layer.
Embodiment 2 to 3
Except the tungsten oxide in the mixture of the tungsten oxide dispersion liquid in embodiment 1 and carbon black dispersion and carbon black
Outside content (wt%) changes as shown in table 1, heat transfer film is prepared in the same manner as example 1.
Embodiment 4
To the butanone as solvent of 100 weight portions, add the polymethyl methacrylate of 25 weight portions, 30 weight portions
Epocryl, trifunctional's acrylate monomer of 8 weight portions, and the initiator of 2 weight portions.Then,
Blend compositions.To the mixture obtained, add carbon black dispersion and the mixing of tungsten oxide dispersion liquid of 60 weight portions
Thing (carbon black dispersion of 50wt%:50wt% and the ratio of tungsten oxide dispersion liquid).Then, mixture is stirred 30
Minute.For tungsten oxide and the dispersion stabilization of carbon black, add the perfluorinated compound (Exfluor of 0.5 weight portion
The 1H of Research Corporation, 1H, 10H, 10H-perfluor-1,10-decyl diacrylate) prepare for photothermal conversion
The compositions of layer.To the butanones of 47.15 grams (MEK) and the mixture of the propylene glycol methyl ether acetate of 26.05 grams, add
Add 17.99 grams the six functionality amine formic acid esters acrylate oligomer as ultraviolet curing resin (Sartomer's
CN9006), the trifunctional's acrylate monomer as polyfunctional monomer (SR351 of Sartomer) of 7.44 grams, and
The 1H as ultraviolet-curing fluorine compounds of 0.62 gram, 1H, 10H, 10H-perfluor-1,10-decanediol diacrylate
(Exfuluor Research Corportation).Then, mixture is stirred 30 minutes.Thereafter, the work of 0.75 gram is added
For the Irgacure 184 (Basf) of initiator, and the compositions that last stirring preparation in 30 minutes is for intermediate layer.The use prepared
In heat conversion layer compositions use No. 8 bars and rod is applied on PET film, appliance at 80 DEG C be dried 2 minutes.
Then, compositions for intermediate layer uses No. 8 bars and rod is coated with, and appliance is dried 2 minutes at 80 DEG C, and
With 300mJ/cm under ultraviolet2Solidification, it is thus achieved that comprise basal layer, heat conversion layer intermediate layer heat transfer film (film thickness:
3μm)。
Comparative example 1 to 5
Except at the tungsten oxide of embodiment 1 of 35 weight portions and the tungsten oxide in the mixture of carbon black and the ratio of carbon black
Outside rate (wt%) changes as shown in table 1, heat transfer film is prepared in the same manner as example 1.
The evaluation of physical property
Evaluate the following character of the heat transfer film system of embodiment and comparative example, and result is shown in table 1.
(1) OD value: use Perkin Elmer Lambda 1050UV/VIS spectrogrph in the ripple of 850nm and 1100nm
On heat transfer film, OD value is measured under length.
(2) OD value deviation: use following equation for each OD value meter measured under the wavelength of 850nm and 1100nm
Calculation OD value deviation:
OD value deviation=[(| measure OD value-target OD value |)/target OD value] Ⅹ 100.
Herein, the target OD value of embodiment 1 to 4 and comparative example 1 to 5 is under the wavelength of 850nm and the wavelength of 1100nm
Similarly it is set to 1.20.
(3) outward appearance: by naked eyes by reflecting mirror or with transmission mode inspection heat conversion layer.Feelings in coating uniform distribution
Under condition, evaluated for appearance is ' good ', and for ' poor ' in the case of observing spot or stain.
(4) transfer efficiency: luminescent material is deposited on the heat transfer film of preparation, and there is the sample of 1cm x 1cm size
It is exposed to laser.By microscope, in the case of the luminescent material 80% or the most deposited is transferred, through swashing
The part of light exposure is assessed as ' good ', and in the case of the deposited luminescent material less than 80% is transferred for '
Difference '.
Table 1
As shown in table 1 and Fig. 3, the heat transfer film of the present invention have 4% or less under the wavelength of 850nm measure
OD value and the OD value measured under the wavelength of 1100nm are relative to the deviation of target OD value, and at 850nm to 1100
The OD value measured under the wavelength of nm is the most homogeneous.Additionally, the heat transfer film of the present invention have excellence transfer efficiency and
Outward appearance.
On the other hand, in comparative example 1 and 5, wherein, carbon black or tungsten oxide are used alone, such as table 1 and Fig. 3 institute
Show, it was demonstrated that heat transfer film have the OD value deviation more than 4% and under whole wavelength inhomogenous OD value.Additionally, work as
When the content of carbon black and tungsten oxide uses in a large number, irradiate with the laser of the wavelength of 850nm and 1100nm, heat transfer film
There is poor transfer efficiency and outward appearance.And, in comparative example 2 to 4, wherein, carbon black and tungsten oxide are used,
But their content is not within the scope of the invention, heat transfer film also has poor transfer efficiency and outward appearance.
Claims (16)
1. a heat transfer film, comprises:
Basal layer, and
Being formed at the heat conversion layer on described basal layer, described heat conversion layer comprises carbon black and tungsten oxide,
Wherein, described heat transfer film has an optical density value deviation represented with equation 1 of 4% or less:
[equation 1]
OD value deviation=[(| measure OD value-target OD value |)/target OD value] × 100
Wherein, measuring OD value is the OD value measured under the wavelength of 850nm and the wavelength of 1100nm respectively.
Heat transfer film the most according to claim 1, wherein, based on described carbon black and the total amount of described tungsten oxide,
Described carbon black exists with the amount of about 25wt% to about 55wt%, and described tungsten oxide with about 45wt% to about 75wt%'s
Amount exists.
Heat transfer film the most according to claim 1, wherein, described carbon black and described tungsten oxide have about 1:1
Mean diameter ratio to about 1:2.
Heat transfer film the most according to claim 1, wherein, described carbon black has about 40nm to about 200nm
Mean diameter, and described tungsten oxide has the about 20nm mean diameter to about 200nm.
Heat transfer film the most according to claim 1, wherein, described carbon black and described tungsten oxide are with about 15wt%
Amount to about 55wt% is present in described heat conversion layer.
Heat transfer film the most according to claim 1, wherein, according to ASTM D2414, described carbon black has about
The oil factor (OAN) of 50cc/100g to about 120cc/100g.
Heat transfer film the most according to claim 1, further contained in the intermediate layer on described heat conversion layer.
Heat transfer film the most according to claim 1, wherein, described heat transfer film have 0.3 or less with side
Formula 2 represent under the wavelength of 850nm measure OD value with under the wavelength of 1100nm measurement OD value it
Between OD value difference different (△ OD):
[equation 2]
△ OD=| the OD value of the measurement of OD value-under 1100nm measured under 850nm |.
9. a heat transfer film, comprises:
Basal layer, and
Being formed at the heat conversion layer on described basal layer, described heat conversion layer comprises carbon black and tungsten oxide,
Wherein, described heat transfer film has the survey under the wavelength of 850nm represented with equation 2 of 0.05 or less
OD value difference different (△ OD) between OD value and the OD value measured under the wavelength of 1100nm of amount:
[equation 2]
△ OD=| the OD value that the OD value measured under 850nm is measured under 1100nm |.
Heat transfer film the most according to claim 9, wherein, based on described carbon black and described tungsten oxide total
Amount, described carbon black exists with the amount of about 25wt% to about 55wt%, and described tungsten oxide is with about 45wt% to about 75wt%
Amount exist.
11. heat transfer films according to claim 9, wherein, described carbon black and described tungsten oxide have about 1:1
Mean diameter ratio to about 1:2.
12. heat transfer films according to claim 9, wherein, described carbon black has about 40nm to about 200nm
Mean diameter, and described tungsten oxide has the about 20nm mean diameter to about 200nm.
13. heat transfer films according to claim 9, wherein, described carbon black and described tungsten oxide are with about 15wt%
Amount to about 55wt% is present in described heat conversion layer.
14. heat transfer films according to claim 9, wherein, according to ASTM D2414, described carbon black has
The oil factor (OAN) of about 50cc/100g to about 120cc/100g.
15. heat transfer films according to claim 9, further contained in the intermediate layer on described heat conversion layer.
16. 1 kinds of Organnic electroluminescent devices, use according to the heat transfer film according to any one of claim 1 to 15
Prepare as donor membrane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130146687A KR20150062090A (en) | 2013-11-28 | 2013-11-28 | Thermal transfer film and electroluminescence display device prepared using the same |
| KR10-2013-0146687 | 2013-11-28 | ||
| PCT/KR2014/011495 WO2015080493A1 (en) | 2013-11-28 | 2014-11-27 | Thermal transfer film and organic electroluminescence element fabricated using same |
Publications (1)
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|---|---|
| CN105980161A true CN105980161A (en) | 2016-09-28 |
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|---|---|---|---|
| CN201480065094.9A Pending CN105980161A (en) | 2013-11-28 | 2014-11-27 | Thermal transfer film and organic electroluminescence element fabricated using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2016538700A (en) |
| KR (1) | KR20150062090A (en) |
| CN (1) | CN105980161A (en) |
| TW (1) | TW201529337A (en) |
| WO (1) | WO2015080493A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741287A (en) * | 2017-06-19 | 2020-01-31 | 住友金属矿山株式会社 | Photothermal conversion layer, method for producing same, and donor sheet using photothermal conversion layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100579174B1 (en) * | 2003-12-22 | 2006-05-11 | 삼성에스디아이 주식회사 | Donor film for laser induced thermal imaging method and electroluminescence display device manufactured using the same film |
| KR100686342B1 (en) * | 2003-11-29 | 2007-02-22 | 삼성에스디아이 주식회사 | Thermal Transfer Element with LTHC having gradient concentration |
| KR20120074116A (en) * | 2010-12-27 | 2012-07-05 | 제일모직주식회사 | Thermal transfer film |
| CN103158386A (en) * | 2011-12-16 | 2013-06-19 | 第一毛织株式会社 | Thermal transfer film and method of manufacturing OLED display |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002096568A (en) * | 2000-09-26 | 2002-04-02 | Dainippon Printing Co Ltd | Thermal transfer film |
| KR100579191B1 (en) * | 2004-02-24 | 2006-05-11 | 삼성에스디아이 주식회사 | Thermal Transfer Element |
| JP2007076069A (en) * | 2005-09-12 | 2007-03-29 | Fujifilm Corp | Manufacturing method of optical sheet for display |
-
2013
- 2013-11-28 KR KR1020130146687A patent/KR20150062090A/en not_active Application Discontinuation
-
2014
- 2014-11-27 CN CN201480065094.9A patent/CN105980161A/en active Pending
- 2014-11-27 WO PCT/KR2014/011495 patent/WO2015080493A1/en active Application Filing
- 2014-11-27 JP JP2016534954A patent/JP2016538700A/en active Pending
- 2014-11-28 TW TW103141426A patent/TW201529337A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100686342B1 (en) * | 2003-11-29 | 2007-02-22 | 삼성에스디아이 주식회사 | Thermal Transfer Element with LTHC having gradient concentration |
| KR100579174B1 (en) * | 2003-12-22 | 2006-05-11 | 삼성에스디아이 주식회사 | Donor film for laser induced thermal imaging method and electroluminescence display device manufactured using the same film |
| KR20120074116A (en) * | 2010-12-27 | 2012-07-05 | 제일모직주식회사 | Thermal transfer film |
| CN103158386A (en) * | 2011-12-16 | 2013-06-19 | 第一毛织株式会社 | Thermal transfer film and method of manufacturing OLED display |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741287A (en) * | 2017-06-19 | 2020-01-31 | 住友金属矿山株式会社 | Photothermal conversion layer, method for producing same, and donor sheet using photothermal conversion layer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015080493A1 (en) | 2015-06-04 |
| TW201529337A (en) | 2015-08-01 |
| JP2016538700A (en) | 2016-12-08 |
| KR20150062090A (en) | 2015-06-05 |
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