CN113736309A - Photocurable ink composition, sealing layer, and image display device - Google Patents
Photocurable ink composition, sealing layer, and image display device Download PDFInfo
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- CN113736309A CN113736309A CN202110591267.2A CN202110591267A CN113736309A CN 113736309 A CN113736309 A CN 113736309A CN 202110591267 A CN202110591267 A CN 202110591267A CN 113736309 A CN113736309 A CN 113736309A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
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Abstract
The present invention provides a photocurable ink composition comprising a siloxane compound having a specific structure, a photocurable monomer, and a photopolymerization initiator, an encapsulation layer comprising a cured product thereof, and an image display device comprising the encapsulation layer. The photocurable ink composition according to the present invention includes a siloxane compound having a specific structure and has a low dielectric constant, and thus does not decrease a signal speed. Further, the photocurable ink composition according to the present invention achieves low viscosity by using a photocurable monomer as a diluent without using a solvent, so that fine patterning can be performed by inkjet printing.
Description
Technical Field
The present invention relates to a photocurable ink composition, an encapsulation layer, and an image display device, and more particularly, to a photocurable ink composition that can be finely patterned by inkjet printing because it has a low dielectric constant without slowing down signal speed and can achieve low viscosity, an encapsulation layer including a cured product thereof, and an image display device including the encapsulation layer.
Background
In an Organic Light Emitting Device (OLED), an organic emission layer is formed for each pixel, and an encapsulation layer for protecting the organic emission layer from external impurities or moisture may be formed.
As the encapsulation layer, an inorganic encapsulation layer including silicon oxide, silicon nitride, and/or silicon oxynitride may be formed. However, the use of only an inorganic encapsulating layer may not be sufficient to prevent deterioration of the display element due to external moisture. Therefore, it is conceivable to form an additional organic encapsulation layer using the photocurable composition.
Recently, as the resolution of OLED devices is improved, the pattern and pixel size are also increasingly finer. Therefore, the photocurable composition is also required to have physical properties suitable for fine coating or fine patterning.
Korean patent laid-open No. 10-1359470 discloses a photocurable composition comprising an alkali-soluble resin, a photocurable monomer, a photopolymerization initiator, a p-dimethylaminobenzoyl or aminobenzoyl hydrogen donor, and a solvent, and having improved photoreactivity by activating an alkyl group generated by the photopolymerization initiator.
However, since the photocurable composition includes an alkali-soluble resin and increases in viscosity, there is a limitation in achieving desired fine patterning.
On the other hand, the amount of information traffic handled is rapidly increasing, as represented by the spread of transmission of moving images via optical communication lines and wireless communication lines. Therefore, it is required to increase the speed of the image display device, and in order to increase the speed, it is required to lower the dielectric constant to reduce the storage capacity of the encapsulation layer.
Korean patent laid-open No. 10-1826020 discloses a solvent-free photocurable inkjet composition including a backbone containing a heteroatom and a branch chain bonded to the backbone and containing at least one nitrogen atom and generating a gas by light irradiation, and the backbone containing the heteroatom has a benzocarbazole structure or a phenylthiophenyl phenyl structure.
However, since the photocurable inkjet composition does not consider ensuring a low dielectric constant, it may be difficult to increase the speed of an image display device.
Therefore, there is an urgent need to develop a photocurable ink composition having a low dielectric constant without decreasing signal speed and realizing a low viscosity so that fine patterning can be performed by inkjet printing.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a photocurable ink composition which can perform fine patterning by inkjet printing without decreasing a signal speed and can realize a low viscosity due to a low dielectric constant.
Another object of the present invention is to provide an encapsulant comprising a cured product of the photocurable ink composition.
Another object of the present invention is to provide an image display device including the encapsulation layer.
Technical scheme
In one aspect, the present invention provides a photocurable ink composition comprising a compound of the following chemical formula 1, a photocurable monomer, and a photopolymerization initiator.
[ chemical formula 1]
In the chemical formula 1, the first and second organic solvents,
r is each independently C1-C30The alkyl group of (a) is,
a is an integer of 0 to 15.
The photocurable ink composition according to one embodiment of the present invention may have a viscosity of 10 to 30cP at 25 ℃, and a dielectric constant of a cured film may be 3.0 or less.
In one embodiment of the present invention, the compound of chemical formula 1 may be contained in an amount of 1 to 60% by weight, relative to 100% by weight of the total of the photocurable ink composition.
In one embodiment of the present invention, the photocurable monomer may include at least one of the compounds represented by the following chemical formulas 2-1 to 2-5.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
In the chemical formula, the compound represented by the formula,
R1each independently of the other is hydrogen or methyl,
R2is C1-C30Alkyl or C3-C30The cycloalkyl group of (a) is,
R3is hydrogen or C1-C3The alkyl group of (a) is,
R4is hydrogen, hydroxy, C1-C3Alkyl or C1-C3The alkoxy group of (a) is (b),
l is C2-C20The alkylene group of (a) is,
n is an integer of 0 to 10, respectively.
In the photocurable ink composition according to one embodiment of the present invention, 10 to 80% by weight of the monofunctional photocurable monomer, 10 to 40% by weight of the difunctional photocurable monomer, and 5 to 40% by weight of the tri-to tetra-functional photocurable monomer may be included, relative to 100% by weight of the total of the photocurable ink composition.
In the photocurable ink composition according to one embodiment of the present invention, the content of the solvent is 1 wt% or less.
The photocurable ink composition according to one embodiment of the present invention may be used for encapsulation of an organic light emitting device.
In another aspect, the present invention provides an encapsulant layer comprising a cured product of the photocurable ink composition.
In yet another aspect, the present invention provides an image display device including the encapsulation layer.
Technical effects
The photocurable ink composition according to the present invention includes a siloxane compound having a specific structure and has a low dielectric constant of 3.0 or less, and thus does not decrease a signal speed. Further, the photocurable ink composition according to the present invention can achieve a low viscosity of 10 to 30cP at 25 ℃ by using a photocurable monomer as a diluent without using a solvent, so that fine patterning can be performed by inkjet printing. Therefore, the photocurable ink composition according to the embodiment of the invention may be advantageously used for encapsulation (encapsulation) of an organic light emitting device.
In addition, the photocurable ink composition according to the embodiment of the invention may have excellent gas and moisture barrier properties after curing, and may have improved curability and stability.
Detailed Description
Hereinafter, the present invention will be described in more detail.
One embodiment of the present invention relates to a photocurable ink composition including a siloxane compound (a), a photocurable monomer (B), and a photopolymerization initiator (C).
The photocurable ink composition according to one embodiment of the present invention may have a viscosity of 10 to 30cP at 25 ℃. If the viscosity is less than 10cP at 25 ℃, jetting difficulty may occur during jetting, and if it exceeds 30cP, jetting property may be poor.
In the photocurable ink composition according to one embodiment of the present invention, the dielectric constant of the cured film may be 3.0 or less, preferably 2.7 or less.
The dielectric constant is a physical unit representing the influence of the medium between charges thereof on the electric field when the electric field acts between the charges, and may also be regarded as an amount of charge that the medium can store.
The dielectric constant of the cured film of the photocurable ink composition according to one embodiment of the present invention is a value measured at a frequency of 100kHz for a sample of the cured film having a thickness of 8 μm after curing, according to the method described in the experimental example described later.
The dielectric constant of the cured film may be 3.0 or less, for example, more than 1 and not more than 3.0, preferably more than 1 and not more than 2.7. When the dielectric constant of the cured film is greater than 3.0, the signal speed may be slow.
The photocurable ink composition according to one embodiment of the present invention has a low dielectric constant of 3.0 or less and does not decrease a signal rate, and can achieve a low viscosity of 10 to 30cP at 25 ℃ using a photocurable monomer as a diluent, so that fine patterning can be performed by inkjet printing. Therefore, the photocurable ink composition according to one embodiment of the present invention may be advantageously used for encapsulation of an organic light emitting device.
Siloxane compound (A)
In one embodiment of the present invention, the siloxane compound (a) is a compound represented by the following chemical formula 1, which is used to reduce the dielectric constant of the photocurable ink composition and also advantageously achieve low viscosity.
[ chemical formula 1]
In the chemical formula, the compound represented by the formula,
r is each independently C1-C30The alkyl group of (a) is,
a is an integer of 0 to 15.
C as used herein1-C30The alkyl group of (b) means a straight-chain or branched-chain hydrocarbon composed of 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecanoyl, nonadecyl, eicosyl, docosyl and the like, but is not limited thereto.
In one embodiment of the present invention, R may preferably be C1-C12More preferably C1-C6Most preferably methyl. When R is C1-C12The alkyl group (b) is preferable from the viewpoint of achieving low viscosity, and thus the sprayability can be improved.
In one embodiment of the present invention, a is an integer of 0 to 15, preferably 0 to 10. When a exceeds the above range, the ejection property may be deteriorated due to the increase in viscosity.
Specific examples of the compound of the above chemical formula 1 include 1, 3-divinyltetramethyldisiloxane and the like, and DMS-V03, DMS-V05 and the like such as those available from Gelest can be used as commercially available products.
The content of the compound of chemical formula 1 is 1 to 60% by weight, preferably 1 to 30% by weight, relative to 100% by weight of the total of the photocurable ink composition. If the content of the compound of chemical formula 1 is less than 1% by weight, the dielectric constant may increase and the film hardness may be insufficient, and if it exceeds 60% by weight, the ejection property may be deteriorated.
Photocurable monomer (B)
In one embodiment of the present invention, the photocurable monomer (B) may be a monofunctional photocurable monomer, a bifunctional photocurable monomer, a tri-to tetra-functional photocurable monomer, or the like as a compound that is polymerized by the action of light and a photopolymerization initiator described below.
The photocurable monomer is preferably at least one of a monofunctional photocurable monomer represented by the following chemical formula 2-1, a bifunctional photocurable monomer represented by the following chemical formulae 2-2 to 2-3, and three to four functional photocurable monomers represented by the following chemical formulae 2-4 to 2-5.
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
In the chemical formula
R1Each independently of the other is hydrogen or methyl,
R2is C1-C30Alkyl or C3-C30The cycloalkyl group of (a) is,
R3is hydrogen or C1-C3The alkyl group of (a) is,
R4is hydrogen, hydroxy, C1-C3Alkyl or C1-C3The alkoxy group of (a) is (b),
l is C2-C20The alkylene group of (a) is,
n is an integer of 0 to 10, respectively.
As used herein C3-C30The cycloalkyl group of (b) means a simple or fused cyclic hydrocarbon consisting of 3 to 30 carbon atoms, and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., but is not limited thereto.
As used herein C1-C3The alkyl group of (b) means a straight or branched monovalent hydrocarbon consisting of 1 to 3 carbon atoms, and includes, for example, methyl, ethyl, n-propyl, isopropyl, etc., but is not limited thereto.
As used herein C1-C3The alkoxy group of (b) means a straight or branched alkoxy group consisting of 1 to 3 carbon atoms, and includes methoxy, ethoxy, n-propoxy and the like, but is not limited thereto.
C as used herein2-C20The alkylene group of (a) means a linear or branched divalent hydrocarbon consisting of 2 to 20 carbon atoms, and includes, for example, ethylene, n-propylene, iso-propylene, n-butene, iso-butene, n-pentene, n-hexene, n-heptene, n-octene, n-nonene, 1-methylheptene, etc., but is not limited thereto.
C1-C30Alkyl of (C)3-C30Cycloalkyl of, C1-C3Alkyl of (C)1-C3Alkoxy and C2-C20One or more hydrogens of the alkylene group of (a) may be replaced by: c1-C6Alkyl of (C)2-C6Alkenyl of, C2-C6Alkynyl of (A), C3-C10Cycloalkyl of, C3-C10Heterocycloalkyl of (A), C3-C10Heterocyclic alkoxy of (A), C1-C6Halogenoalkyl of, C1-C6Alkoxy group of (C)1-C6Thioalkoxy ofAryl, acyl, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro and the like.
In one embodiment of the invention, R2May preferably be C7-C30Alkyl or C7-C30More preferably C10-C25Alkyl or C7-C25A cycloalkyl group of (a). When R is2Is C7-C30Alkyl or C7-C30Is preferable in terms of achieving a low dielectric constant and a low viscosity.
Specific examples of the compound represented by the chemical formula 2-1 include dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
Specific examples of the compound represented by chemical formula 2-2 include 1, 4-bis ((meth) acryloyloxy) butane, 1, 6-hexanediol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and the like.
Specific examples of the compound represented by chemical formula 2-3 include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and the like.
Specific examples of the compounds represented by chemical formulas 2 to 4 include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.
Specific examples of the compound represented by chemical formula 2 to 5 include pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, and the like.
The photo-curable ink composition according to one embodiment of the present invention may include the monofunctional photo-curable monomer in an amount of 10 to 80% by weight, relative to 100% by weight of the total photo-curable ink composition, in terms of achieving low viscosity. If the content of the monofunctional photocurable monomer is less than 10 wt%, the viscosity of the photocurable ink composition may increase and the ejection property may be deteriorated, and if it exceeds 80 wt%, ejection difficulty may occur during the ejection.
In the photocurable ink composition according to one embodiment of the present invention, the content of the bifunctional photocurable monomer may be 10 to 40% by weight with respect to 100% by weight of the total photocurable ink composition. If the content of the bifunctional photocurable monomer is less than 10 wt%, the pencil hardness may decrease, and if it is more than 40 wt%, the ejection property may be deteriorated.
In the photocurable ink composition according to one embodiment of the present invention, the content of the three-to four-functional photocurable monomer may be 5 to 40% by weight with respect to 100% by weight of the total photocurable ink composition. When the content of the tri-to tetrafunctional photocurable monomer is less than 5% by weight, the pencil hardness may decrease, and when it is more than 40% by weight, the viscosity may increase and the ejection property may be deteriorated.
Photopolymerization initiator (C)
In one embodiment of the present invention, a photopolymerization initiator (C) may be used without particular limitation on its kind as long as it can polymerize the photocurable monomer. In particular, the photopolymerization initiator (C) is preferably at least one compound selected from the group consisting of the following compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price: acetophenone compounds, benzophenone compounds, triazine compounds, bisimidazole compounds, oxime compounds, and thioxanthone compounds.
Specific examples of the acetophenone compounds include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl ] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propan-1-one, and mixtures thereof, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzophenone, and the like.
Specific examples of the triazine compounds include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperidyl 1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyrene) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan) -2-yl) vinyl ] -triazine 1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.
Specific examples of the biimidazole compound may include 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetrakis (trialkoxyphenyl) biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole or a compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group, and the like. Among them, 2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2' -bis (2, 3-dichlorophenyl) -4,4',5,5' -tetraphenyl biimidazole, 2-bis (2, 6-dichlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole are preferably used.
Specific examples of the oxime compounds include o-ethoxycarbonyl- α -oxyimino-1-phenylpropan-1-one and the like, and Irgacure OXE 01 and OXE 02 of basf are representative as commercially available products.
Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
The content of the photopolymerization initiator (C) may be 1 to 10% by weight, preferably 1 to 5% by weight, relative to 100% by weight of the total photocurable ink composition. When the photopolymerization initiator is contained within the above range, the photocurable ink composition is highly sensitive, and thus the exposure time is shortened, so that productivity can be improved. In addition, the following advantages are provided: the strength of a cured film formed using the photocurable ink composition according to the present invention and the smoothness of the surface of the cured film are improved.
Additive (D)
The photocurable ink composition according to one embodiment of the present invention may further include additives such as a surfactant, a tackifier, and the like, in addition to the above components, to improve flatness or adhesiveness of a coating film.
When the photocurable ink composition according to the present invention contains a surfactant, there is an advantage that the flatness of the coating film can be improved. For example, as the surfactant, a fluorine-based surfactant such as BM-1000, BM-1100(BM Chemie), Prolide FC-135/FC-170C/FC-430(Sumitomo 3M Co., Ltd.), SH-28PA/-190/-8400/SZ-6032(Toray Co., Ltd.), Efka FL 3600 (BASF) can be used, but not limited thereto.
The tackifier may be added to increase adhesion to the substrate, and may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, (meth) acryl group, an isocyanate group, an epoxy group, and a combination thereof, but is not limited thereto. For example, the silane coupling agent may be exemplified by trimethoxysilylbenzoic acid, γ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.
Further, the photocurable ink composition according to the present invention may further contain additives such as an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent within a range that does not hinder the effects of the present invention, and the additives may also be appropriately added and used by those skilled in the art within a range that does not hinder the effects of the present invention.
The amount of the additive may be used in 0.05 to 10 wt%, specifically 0.1 to 10 wt%, and more specifically 0.1 to 5 wt%, relative to the total 100 wt% of the photocurable ink composition, but is not limited thereto.
The photocurable ink composition according to one embodiment of the present invention contains substantially no solvent, and even if it contains a solvent, the content of the solvent is 10 wt% or less with respect to 100 wt% of the total photocurable ink composition. The photocurable ink composition according to one embodiment of the present invention can realize a low viscosity even when it is a solventless type containing no solvent or a low-solvent type containing 5 wt% or less (for example, 1 wt% or less).
The photocurable ink composition according to one embodiment of the present invention contains substantially no resin component, and even if the resin component is contained, the resin component is contained in an amount of 1 wt% or less, preferably 0.5 wt% or less, relative to 100 wt% of the total photocurable ink composition. Since the photocurable ink composition according to one embodiment of the present invention does not contain a resin component, a low viscosity can be achieved, and the nozzle ejection characteristics of the ink are excellent.
In addition, the photocurable ink composition according to one embodiment of the present invention may have excellent gas and moisture barrier properties after curing.
Also, the photocurable ink composition according to the present invention may have improved curability and stability.
One embodiment of the present invention relates to an encapsulating layer comprising a cured product of the above photocurable ink composition.
The encapsulation layer serves to prevent oxidation or decomposition of the surface of the member for a device caused by external environment such as moisture and oxygen by sealing the member for a device.
The method of forming a pattern of the photocurable ink composition according to the present invention includes the steps of: applying a photocurable ink composition to a predetermined region by an inkjet method; and curing the applied photocurable ink composition.
First, the photocurable ink composition of the present invention is injected into an inkjet spray machine to perform printing on a predetermined region of a member for a device.
In order to eject from a piezoelectric inkjet head as an example of an inkjet sprayer to form an appropriate phase on a member for a device, characteristics such as viscosity and fluidity must be balanced with the inkjet head. The piezoelectric inkjet head used in the present invention is not limited, but ejects ink having a droplet size of about 10 to 100pL (preferably about 20 to 40 pL).
One embodiment of the present invention relates to an image display device including the above encapsulation layer.
The image display device may include a device member and a barrier stack formed on the device member, the barrier stack including an inorganic encapsulation layer and an organic encapsulation layer, the organic encapsulation layer including a cured product of the above photocurable ink composition.
The member for a device may be decomposed, oxidized or degraded when exposed to an external environment such as moisture or oxygen, and examples thereof include an organic light emitting device, a liquid crystal panel, and the like.
The device-use member may be formed on a substrate.
The substrate is not limited, and the following substrates having a flat surface can be exemplified: a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide imide substrate, a polyimide substrate, an Al substrate, a GaAs substrate, and the like. These substrates may be pretreated as follows: chemical treatment with a chemical agent such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, vacuum evaporation treatment, and the like. When a silicon substrate or the like is used as the substrate, a Charge Coupled Device (CCD), a Thin Film Transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like. Further, a partition wall matrix may be formed.
The inorganic encapsulation layer is used together with the organic encapsulation layer to protect the device member from external environments such as moisture and oxygen. The inorganic encapsulating layer has a different composition from the organic encapsulating layer and contains an inorganic component as a main component. For example, the inorganic encapsulation layer may include: metals or non-metals such as silicon (Si), aluminum (Al), selenium (Se), zinc (Zn), antimony (Sb), indium (In), germanium (Ge), tin (Sn), bismuth (Bi), transition metals, and lanthanoid metals; compounds between these metals or non-metals; alloys of these metals or non-metals; oxides of these metals or non-metals; nitrides of these metals or nonmetals; oxynitrides of these metals or non-metals, and the like.
The image display device may be an Organic Light Emitting Device (OLED), a liquid crystal display device (LCD), an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), or the like, but is not limited thereto. In particular, the image display device may be an Organic Light Emitting Device (OLED).
Hereinafter, the present invention will be described in more detail by examples, comparative examples and experimental examples. These examples, comparative examples and experimental examples are only for illustrating the present invention, and it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.
Examples and comparative examples: preparation of Photocurable ink composition
Photocurable ink compositions (wt%) were prepared by mixing the components in the compositions of tables 1 and 2 below.
[ Table 1]
[ Table 2]
A-1: 1, 3-Divinyltetramethyldisiloxane (TCI Co.)
A-2: DMS-V03(Gelest, molecular weight 500)
A-3: DMS-V05(Gelest, molecular weight 800)
A-4: hydroxy-terminated poly (dimethylsiloxane) (481939 Aldrich)
B-1: dodecyl acrylate (TCI Co., Ltd.)
B-2: octadecanoyl acrylate (TCI Co., Ltd.)
B-3: 1, 4-bis (acryloyloxy) butane (TCI Co.)
B-4: 1, 6-hexanediol diacrylate (A-HD-N, Xinzhongcun)
B-5: isononanediol diacrylate (A-IND, Xinzhongcun)
B-6: dipropylene glycol diacrylate (APN-100, Xinzhongcun)
B-7: trimethylolpropane triacrylate (A-TMPT, Xinzhongcun)
B-8: ethoxylated pentaerythritol tetraacrylate (EO 4 mol) (ATM-4E, Xinzhongcun)
B-9: acrylic acid ethyl ester
B-10: acrylic acid propyl ester
C-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Igacure 369, Basff)
D-1: efka FL 3600 (Basff corporation)
Experimental example:
using the photocurable ink compositions prepared in the examples and comparative examples, the following physical properties were evaluated in the following manner, and the results thereof are shown in table 3 below.
(1) Viscosity of the solution
The viscosity of each of the photocurable ink compositions prepared in examples and comparative examples was measured using a viscometer (DV3T, manufactured by Brookfield corporation) (measurement conditions: rotation speed 20rpm/25 ℃ C.).
(2) Hardness of pencil
Each of the photocurable ink compositions prepared in examples and comparative examples was coated on a glass substrate by an inkjet method and then cured using a UV curing apparatus (Lichtzen Corp., model LZ-UVC-F402-CMD) at 150mW/cm2Was irradiated with ultraviolet rays for 120 seconds at an illuminance of 320-400nm in the UV-A region to prepare a photocurable film.
The pencil hardness of the prepared photocurable film was measured using a pencil hardness meter. Specifically, after a pencil (manufactured by mitsubishi corporation) was brought into contact with the photo-cured film, the surface hardness was measured by scratching the surface with a load of 1kg and a speed of 50 mm/sec.
(3) Ink jet characteristics
Each of the photocurable ink compositions prepared in examples and comparative examples was printed using an Omnijet 100 inkjet printer manufactured by Unijet corporation. During the injection, it was observed whether injection difficulty occurred. In addition, after pattern printing was performed in an area of 500dpi and length × width (50mm × 50mm), the shape of the organic film was observed. The ink ejection performance was evaluated according to the following evaluation criteria.
< evaluation criteria >
O: the spraying difficulty and the pinhole cannot occur in the spraying process.
And (delta): some jetting difficulties may occur when jetting, or fewer than two pinholes may occur.
X: when spraying, serious difficulty in spraying may occur, or more than three pinholes may be generated.
(4) Dielectric constant
Each of the photocurable ink compositions prepared in examples and comparative examples was cured on a boron-doped P-type silicon wafer and coated to a thickness of 8 μm, exposed to light under a UV LED at 395nm, and then a circular aluminum thin film having a diameter of 1mm was deposited on the wafer using a hard mask designed to have a diameter of 1mm
To complete the measurement forA thin film of metal-insulator-metal (MIM) structure. The capacitance of each of these films was measured at a frequency of about 100kHz using a PRECISION LCR METER (HP4284A) equipped with a probe station (micromanipulator 6200 probe station). After measuring the thickness of the thin film with an ellipsometer, the dielectric constant was calculated by substituting it into the following equation 1.
[ equation 1]
k＝(C×A)/(εo×d)
In the above equation, k is the dielectric ratio, C is the capacitance, ε o is the dielectric constant of vacuum, d is the thickness of the film, and A is the contact cross-sectional area of the electrode.
(5) Stability of
The viscosity change rate after 1 week of storage at 40 ℃ was calculated by comparing with the initial viscosity of the photocurable ink compositions prepared in the examples and comparative examples to evaluate the stability according to the following evaluation criteria.
< evaluation criteria >
O: the viscosity change rate is within 110 percent.
And (delta): the viscosity change rate is more than 110% and less than 120%.
X: the viscosity change rate exceeds 120 percent.
[ Table 3]
As shown in table 3, it was confirmed that the cured films of the photocurable ink compositions of examples 1 to 14, which included the siloxane compound of chemical formula 1 according to the present invention, had a dielectric constant of 3.0 or less, exhibited a low dielectric constant, had a low viscosity, and also had excellent ink jet characteristics. Further, it can be confirmed that the photocurable ink compositions of examples 1 to 14 including the siloxane compound of formula 1 according to the present invention have excellent curability, improved pencil hardness, and excellent stability over time.
On the other hand, the cured films of the photocurable ink compositions of comparative examples 1 to 5 and 7 to 8, which did not contain the siloxane compound of chemical formula 1, and the photocurable ink composition of comparative example 6, which replaced the siloxane compound of chemical formula 1 with another siloxane compound, had dielectric constants exceeding 3.0, and at least one of ink jet characteristics, degree of curing, and stability over time was poor.
As described above, having described specific portions of the present invention in detail, it will be apparent to those of ordinary skill in the art to which the present invention pertains that these specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Based on the foregoing, those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention.
Accordingly, the substantial scope of the present invention may be defined by the appended claims and equivalents thereof.
Claims (9)
1. A photocurable ink composition comprising a compound of the following chemical formula 1, a photocurable monomer, and a photopolymerization initiator:
[ chemical formula 1]
In the chemical formula 1, the first and second organic solvents,
r is each independently C1-C30The alkyl group of (a) is,
a is an integer of 0 to 15.
2. The photocurable ink composition according to claim 1, wherein the viscosity at 25 ℃ is 10 to 30cP, and the dielectric constant of the cured film is 3.0 or less.
3. The photocurable ink composition according to claim 1, wherein the compound of chemical formula 1 is contained in an amount of 1 to 60% by weight with respect to 100% by weight of the total photocurable ink composition.
4. The photocurable ink composition according to claim 1, wherein the photocurable monomer is at least one compound comprising compounds represented by the following chemical formulae 2-1 to 2-5:
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
In the chemical formula, the compound represented by the formula,
R1each independently of the other is hydrogen or methyl,
R2is C1-C30Alkyl or C3-C30The cycloalkyl group of (a) is,
R3is hydrogen or C1-C3The alkyl group of (a) is,
R4is hydrogen, hydroxy, C1-C3Alkyl or C1-C3The alkoxy group of (a) is (b),
l is C2-C20The alkylene group of (a) is,
n is an integer of 0 to 10, respectively.
5. The photocurable ink composition according to claim 4, characterized by comprising 10 to 80% by weight of the monofunctional photocurable monomer, 10 to 40% by weight of the difunctional photocurable monomer, and 5 to 40% by weight of the tri-to tetra-functional photocurable monomer, relative to 100% by weight of the total photocurable ink composition.
6. The photocurable ink composition according to claim 1, wherein the content of the solvent is 1 wt% or less.
7. The photocurable ink composition according to claim 1, wherein the composition is used for encapsulation of an organic light-emitting device.
8. An encapsulating layer comprising a cured product of the photocurable ink composition according to any one of claims 1 to 7.
9. An image display device comprising the encapsulation layer of claim 8.
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| CN115960490A (en) * | 2022-12-08 | 2023-04-14 | 西安思摩威新材料有限公司 | Photocurable ink composition and preparation method and application thereof |
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