KR101996262B1 - Barrier resin composition, method for uv curable barrier layer and electronic device - Google Patents

Abstract

The present invention relates to a barrier resin composition, a method of manufacturing a photocurable barrier film, and an electronic device. According to the present invention, as a substitute for acrylate decoupling, the transmittance of water and oxygen is low, and flexibility and high toughness applicable to a flexible display are also provided. Decoupling resin comprising a decoupling resin having a, a method for producing a photocuring barrier film having excellent transparency, flexibility, high toughness, oxygen barrier properties and moisture barrier properties, transparency using the barrier resin composition and having such a photocuring barrier film There is an effect to provide an electronic device.

Description

Barrier resin composition, manufacturing method of photocurable barrier film and electronic device {BARRIER RESIN COMPOSITION, METHOD FOR UV CURABLE BARRIER LAYER AND ELECTRONIC DEVICE}

The present invention relates to a barrier resin composition, a method of manufacturing a photocurable barrier film, and an electronic device, and more particularly, has a low transmittance of moisture and oxygen as a substitute for acrylate decoupling, and flexibility and high toughness applicable to a flexible display. A method of manufacturing a photocurable barrier film having excellent transparency, flexibility, high toughness, oxygen barrier property, and moisture barrier property using a barrier resin composition having a barrier, a decoupling resin contained therein, and the barrier resin composition, and the photocuring barrier film It relates to an electronic device having.

In general, an organic electronic device is a device characterized in that when a charge is injected into an organic layer provided between an anode and a cathode, a phenomenon such as light emission or flow of electricity occurs, and a device having various functions may be manufactured according to the selected organic material.

As a representative example, organic light emitting diodes (OLEDs) are attracting attention as next-generation flat panel displays because they are thin, light, and have excellent color, and can be manufactured on existing glass substrates, inorganic substrates including silicon, and metal substrates, as well as plastic substrates, films, or metals. It can also be manufactured on a flexible substrate such as foil, and thus can be manufactured as a flexible display. However, since the organic electronic device is very vulnerable to moisture and oxygen, the luminous efficiency and lifespan are significantly reduced when exposed to the air or when moisture is introduced into the panel from the outside.

Therefore, in order to protect the organic light emitting device from external moisture and oxygen, a barrier layer of the organic material and the metal material is disposed on the upper layer of the organic light emitting device so that the device is not directly exposed to the outside air.

At this time, the barrier layer is not sufficient to prevent the inflow of moisture and oxygen in a single layer. Therefore, by forming one or more barrier layers (barrier stacking process) in a stacked structure of an organic layer (decoupling layer) and an inorganic layer (barrier layer), penetration of moisture and oxygen can be effectively prevented. Wherein the organic layer (decoupling layer) can be formed by methods of deposition and polymerization, and examples of suitable materials for the decoupling layer include organic polymers, inorganic polymers, organometallic polymers, hybrid organic / inorganic polymer systems and silicates. Can be.

Although a thin film barrier composite having a layer of alternating multilayer barrier materials and a decoupling resin is known, an acrylate polymer mainly known as the decoupling resin has a disadvantage in that its transmittance of moisture and oxygen is high. Its disadvantage is that it does not meet the required flexibility and toughness required as a flexible display. In addition, due to the high moisture and oxygen permeability, the number of alternating barrier materials and decoupling resins increases, which increases the number of steps, and the flexibility and high toughness can be satisfied by using a multilayer laminate of decoupling resins having poor flexibility and high toughness. There is a drawback that the cost of display production rises.

For this reason, there is still a need for a decoupling material having a low transmittance of moisture and oxygen and having flexibility and high toughness applicable to a flexible display so as to reduce the number of alternations of the decoupling resin.

Prior document information: Korean Patent Publication No. 2013-0108911

An object of the present invention is to provide a barrier resin composition comprising a decoupling resin having a low permeability of its own moisture and oxygen as a substitute material for an acrylate decoupling resin and having flexibility and high toughness applicable to a flexible display.

Another object of the present invention is to provide a method for producing a photocurable barrier film having excellent transparency, flexibility, high toughness, oxygen barrier property, and moisture barrier property by using the barrier resin composition as a material.

Another object of the present invention is to provide an electronic device having a high barrier encapsulation film as a substitute for a conventional acrylate decoupling encapsulation film.

According to one aspect of the invention, comprising a photocurable silsesquioxane resin (A), a photocurable dimer (B) and a photoinitiator (C), the photocurable silsesquioxane resin (A) and the photocurable The dimer (B) provides a barrier resin composition comprising at least two functional groups selected from the group consisting of a (meth) acryl group, a vinyl group and a mercapto group as each terminal group.

According to another aspect of the present invention, as the photocurable silsesquioxane resin, 2 to 6 functional groups selected from the group consisting of a (meth) acryl group, a vinyl group and a mercapto group at the end of the repeating unit of the silsesquioxane resin It provides a ladder type decoupling resin comprising.

According to another aspect of the present invention, a photocurable silsesquioxane resin (A), a photocurable dimer (B) and a photoinitiator (C) represented by the following Chemical Formula 1 are melted and mixed, coated and dried on a substrate. And forming a blocking lamellar molecular structure by light irradiation, wherein the blocking lamellar molecular structure includes the photocurable dimer (B) as a blocking layer, and the photocurable silsesquioxane resin (A ) Forms a continuous stacked structure on the blocking layer.

[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, R ₂ is a substituted or unsubstituted C ₁ -C ₁₂ alkyl group or a substituted or unsubstituted C _{A 3} -C ₁₈ hydrocarbon ring group, R ₃ is a substituted or unsubstituted C ₃ -C ₁₀ cyclic ether containing hydrocarbon group, and n, m and x are each 0 within a weight average molecular weight of 1,000 to 500,000 g / mol An integer from 100,000 to at least one of n, m and x is not zero, and y and z are each from 0 to 100,00.

According to another aspect of the present invention, there is provided an electronic device comprising a photocurable blocking film prepared from the above-mentioned barrier resin composition.

According to the present invention, there is an effect of providing a barrier resin composition comprising a decoupling resin having a low transmittance of moisture and oxygen as a substitute for acrylate decoupling and having flexibility and high toughness applicable to a flexible display.

According to the present invention, there is an effect of using the barrier resin composition to provide a method for producing a photocurable barrier film excellent in transparency, flexibility, high toughness, oxygen barrier properties and moisture barrier properties.

According to the present invention, there is an effect of providing an electronic device having a high barrier film as a conventional acrylate decoupling substitute.

1 is a schematic diagram showing a lamellar structure according to the present invention, a lamellar laminated structure is connected to a photocurable dimer (corresponding to a straight line notation in the middle) of a silsesquioxane resin (corresponding to a circle notation in the center) of a ladder type. It corresponds to the structure to be formed.

Hereinafter, the present invention will be described in detail.

The present inventors have continued the research to solve the problems of the prior art, as a result, a barrier resin composition comprising a polysilsesquioxane resin that can be bridged to form a photocurable dimer to form a lamellar molecular structure In the case of using, it is confirmed that the photocurable barrier film having excellent transparency, flexibility, high toughness, oxygen barrier property, and moisture barrier property, which can replace the conventionally used acrylate decoupling resin, can be manufactured without alternating many times. Based on this, the present invention has been completed.

The decoupling resin for the barrier resin composition according to the present invention is a photocurable silsesquioxane resin, wherein a functional group selected from the group consisting of a (meth) acryl group, a vinyl group and a mercapto group is formed at the terminal of the repeating unit of the silsesquioxane resin. It is preferable to use ladder resins containing 2 to 6 species because it can provide sufficient flexibility and toughness as the matrix resin when producing the barrier resin composition.

The (meth) acryl group, vinyl group, and mercapto group are photosensitive functional groups capable of causing a curing reaction by exposure under a photoinitiator. Specifically, hydrocarbons containing 3-methacryl, 3-acryl, vinyl, or mercapto groups at their ends. And may be, for example, 3-methacryloxypropyl, 3-acryloxypropyl, 3-methacryl, 3-acryl, vinyl or mercapto group.

For example, the functional group may include a (meth) acryl group at both ends of any repeating unit constituting the silsesquioxane resin.

In addition, the functional group may include a vinyl group at both ends of any repeating unit constituting the silsesquioxane resin.

In addition, the functional group may include a mercapto group at both ends of any repeating unit constituting the silsesquioxane resin.

As a specific example, the photocurable silsesquioxane resin may include a structure represented by the following [Formula 1]:

[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, R ₂ is a substituted or unsubstituted C ₁ -C ₁₂ alkyl group or a substituted or unsubstituted C _{Is a 3} -C ₁₈ hydrocarbon ring group, R ₃ is a substituted or unsubstituted C ₃ -C ₁₀ cyclic ether containing hydrocarbon group, n, m and x are integers from 0 to 100,000, at least of n, m and x One is not zero, and y and z are each an integer of 0 to 100,000.

In one example, R may be a methyl group.

일 수 있다. In one example, R ₁ is a propyl group or

Can be.

,

또는

일 수 있다. In one example, R ₂ is a methyl group,

,

or

Can be.

일 수 있다. In one example, R ₃ is

Can be.

20 to 100 mol%, 25 to 90 mol%, or 30 of at least one (or any one type) repeating unit selected from the first repeating unit, the second repeating unit, and the third repeating unit in the photocurable silsesquioxane resin To 80 mol%, the fourth repeating unit is 0 to 40 mol%, 1 to 30 mol%, or 10 to 30 mol%, and the fifth repeating unit is 0 to 40 mol%, 1 to 30 mol%, or 10 to 30 It may occupy mole%, and in this range, when the photocured silsesquioxane resin is applied to form a barrier film, it may provide mechanical properties such as excellent flexibility and high toughness.

In one example, n, m and x are each an integer of 0 to 100,000, wherein at least one of n, m and x is not zero, and y and z are each from 0 to 100,00. If n, m, x is all 0, as shown in Comparative Example 3 to be described later can not secure excellent oxygen and moisture barrier properties, it can be confirmed that the disadvantages of flexibility and flexible durability due to high curing degree is not good.

In addition, y and z are required in the range of 10 to 30 mol% in the silsesquioxane resin (A) of the present invention, which is to provide physical properties such as chemical resistance, heat resistance, and flexibility of the barrier film. .

As used herein, the term "alkyl" includes straight, branched or cyclic hydrocarbon radicals, and the term "alkylene" refers to a divalent radical derived from alkyl. For example alkylene includes methylene, ethylene, isobutylene, cyclohexylene, cyclopentylethylene, 2-propenylene, 3-butynylene and the like.

"Substituted" in the expression "substituted or unsubstituted" as used herein means that one or more hydrogen atoms in the hydrocarbon are each replaced with the same or different substituents, independently of one another. Useful substituents include, but are not limited to: -Ra, -halo, -O-, = O, -ORb, -SRb, -S-, = S, -NRcRc, = NRb, = N-ORb, tree Halomethyl, -CF ₃ , -CN, -OCN, -SCN, -NO, -NO ₂ , = N ₂ , -N ₃ , -S (O) ₂ Rb, -S (O) ₂ NRb, -S (O) ₂ O-, -S (O) ₂ ORb, -OS (O) ₂ Rb, -OS (O) ₂ O-, -OS (O) ₂ ORb, -P (O) (O-) ₂ , -P (O) (ORb) (O-), -P (O) (ORb) (ORb), -C (O) Rb, -C (S) Rb, -C (NRb) Rb, -C ( O) O-, -C (O) ORb, -C (S) ORb, -C (O) NRcRc, -C (NRb) NRcRc, -OC (O) Rb, -OC (S) Rb, -OC ( O) O-, -OC (O) ORb, -OC (S) ORb, -NRbC (O) Rb, -NRbC (S) Rb, -NRbC (O) O-, -NRbC (O) ORb, -NRbC (S) ORb, -NRbC (O) NRcRc, -NRbC (NRb) Rb and -NRbC (NRb) NRcRc, wherein Ra is alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, arylalkyl, heteroaryl and hetero Arylalkyl; Each R b is independently hydrogen or Ra; And each R c is independently R b or alternatively two R c together with the nitrogen atom to which they are attached form a 4-, 5-, 6- or 7-membered cycloheteroalkyl, which is optionally a group consisting of O, N and S It may comprise 1 to 4 additional heteroatoms same or different selected from. As a specific example, -NRcRc is meant to include -NH ₂ , -NH-alkyl, N-pyrrolidinyl and N-morpholinyl. As another example, substituted alkyl is -alkylene-O-alkyl, -alkylene-heteroaryl, -alkylene-cycloheteroalkyl, -alkylene-C (O) ORb, -alkylene-C (O) NRbRb, and -CH ₂ -CH ₂ -C (O) -CH ₃ . The one or more substituents may be selected with the atoms to which they are attached to form a cyclic ring comprising cycloalkyl and cycloheteroalkyl.

For example, the photocurable silsesquioxane resin may have a weight average molecular weight of 1,000 to 500,000 g / mol, and for example, 11,000 to 16,000 g / mol. Within these ranges, the viscosity of the photocurable silsesquioxane resin is moderate and excellent in workability.

For example, the photocurable silsesquioxane resin may have a polydispersity (PDI) of about 1 to about 5, for example about 1.9 to about 2.5. The flatness of the blocking film formed within these ranges may be excellent.

The barrier resin composition according to an embodiment of the present invention includes a photocurable silsesquioxane resin (A), a photocurable dimer (B) and a photoinitiator (C), wherein the photocurable silsesquioxane resin ( A) and the photocurable dimer (B) are characterized in that they comprise two or more functional groups selected from the group consisting of (meth) acryl groups, vinyl groups and mercapto groups as end groups.

As described above, the photocurable silsesquioxane resin (A) is a ladder-type matrix resin including a structure represented by [Formula 1], and may have a weight average molecular weight of 1,000 to 500,000 g / mol.

The photocurable silsesquioxane resin (A) may provide a moisture and oxygen barrier effect, which can not be provided by the acrylate resin used in the past, at most in two layers alternately.

As a specific example, the photocurable silsesquioxane resin (A) is a ladder type decoupling resin having a repeating unit represented by the following [Formula 2], a ladder type decoupling resin having a repeating unit represented by the following [Formula 3], Ladder type decoupling resin having a repeating unit represented by [Formula 4] And it may be one or more selected from the group consisting of ladder type decoupling resin having a repeating unit represented by the formula [5]:

[Formula 2]

When the repeating unit variable is z, y, n from the left side of Formula 2, z is 0 to 40 mol%, preferably 5 to 35 mol%, y is 0 to 40 mol%, preferably 5 to 25 mol%, n may be 20 to 100 mol%, preferably 30 to 90 mol%.

[Formula 3]

When the repeating unit variable is 1y, 2y, m from the left side of Formula 3, 1y is 0 to 40 mol%, preferably 5 to 35 mol%, 2y is 0 to 40 mol%, preferably 5 to 25 mol%, m may be 20 to 100 mol%, preferably 30 to 90 mol%.

[Formula 4]

When the repeating unit variable is 1y, 3y, x from the left side of Formula 4, 1y is 0 to 40 mol%, preferably 5 to 35 mol%, 3y is 0 to 40 mol%, preferably 5 to 25 mol%, x may be 20 to 100 mol%, preferably 30 to 90 mol%.

[Formula 5]

When the repeating unit variable is 1y, 4y, n from the left side of Formula 5, 1y is 0 to 40 mol%, preferably 5 to 35 mol%, 4y is 0 to 40 mol%, preferably 5 to 25 mol%, n may be 20 to 100 mol%, preferably 30 to 90 mol%.

In Formulas 2, 3, 4, and 5, n, m, x, y, and z are the same as those described in relation to Chemical Formula 1. Ladder type decoupling resin represented by the above [Formula 2], ladder type decoupling resin represented by the above [Formula 3], ladder type decoupling resin represented by the above [Formula 4], and ladder type decoupling represented by the above [Formula 5] The resin may provide different improvement effects in terms of oxygen transmittance, moisture transmittance, curvature radius, and soft durability according to the type of the photocurable dimer (B) to be formulated to form a bridge and blocking layer. By blending, it is possible to optimize the oxygen permeability, moisture permeability, curvature radius, and soft durability.

The photocurable silsesquioxane resin (A) may be, for example, 10 to 90% by weight, 30 to 60% by weight, or 30 to 50% by weight in the total composition, which will be described later as a barrier lamellar structure within this range. Since the photocurable dimer (B) can be used as a blocking layer, it is possible to provide a continuously laminated structure.

The above-mentioned photocurable dimer (B) is at least one selected from the group consisting of a compound represented by the following [Formula 6], a compound represented by the following [Formula 7], and a compound represented by the following [Formula 8]. It is preferable to provide a barrier layer structure for the flame silsesquioxane resin (A), and in particular, it is possible to maximize the barrier effect according to its own hydrophobic properties:

[Formula 6]

[Formula 7]

[Formula 8]

In Formula 6,7,8, R is hydrogen or a methyl group, R ₄ , R ₅ are independently unsubstituted or fluorine-substituted C ₁ -C ₅₀ linear or branched alkylene group, ether group or alkylene oxide Qi.

The photocurable dimer (B) is a specific example, a compound represented by the following [Formula 10], a compound represented by the following [Formula 11], a compound represented by the following [Formula 12], a compound represented by the following [Formula 13] , Using at least one selected from the group consisting of a compound represented by the following [Formula 14] and a compound represented by the following [Formula 15] is a blocking layer structure for the photocurable silsesquioxane resin (A) It is desirable to be able to provide effectively

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The photocurable dimer (B) may be, for example, 10 to 60% by weight, 10 to 30% by weight, or 15 to 30% by weight in the total composition, and the photocurable silsesquioxane resin (A) within this range. And aliphatic hydrophobic monomers are combined during photocuring to sufficiently form a lamellar molecular structure in which the photocurable dimer is bridged, and effectively block moisture and oxygen permeation.

The photoinitiator (C) has a function of initiating polymerization of the crosslinkable unit by wavelengths such as visible light, ultraviolet light and far ultraviolet light. The photoinitiator is, for example, 1-hydroxy-cyclohexylphenyl ketone, benzophenone, 2-benzyl-2- (dimethylamino) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2-methyl-1- (4-methylthio) phenyl-2- (4-morpholinyl) -1-propanone, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis (2 , 4,6-trimethylbenzoyl) phosphine oxide, benzyl-dimethylketal, isopropyl thioxanthone, ethyl (2,4,6-trimethyl benzoyl) phenyl phosphinate and phenyl (2,4,6-trimethyl benzoyl) Phenyl phosphinate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoylperoxide, Lauryl peroxide, t-butylperoxy pivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2- (dimethylamino) -1- [4 -(4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, benzo Paddy, benzoinpropyl ether, diethyl thioxanthone, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1, 3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane- 1,2-dione-2- (O-benzoyloxime), o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide , Hexafluorophosphoro-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and mixtures thereof. As the photoinitiator, if necessary, a chitooxime ester compound and an alpha chitooxime ester compound known in the art may be used in combination or used alone.

The photoinitiator may be 0.1 to 30% by weight, 0.1 to 20% by weight or 0.5 to 10% by weight of the total composition, causing sufficient curing within this range and may also prevent problems such as precipitation due to reduced solubility after curing. .

The barrier resin composition of the present invention may include a crosslinkable unit (D) having at least two ethylenic double bonds. The crosslinkable unit having an ethylene-based double bond is ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol di Acrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylol Propane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, Pentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardoepoxy diacrylate Polyfunctional (meth) acrylic monomers and oligomers, including; (Meth) acrylic acid is reacted with a compound (meth) acrylate obtained by reacting (meth) acrylic acid to a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, and a compound having a polyol group and two isocyanate groups. Polyurethane (meth) acrylate obtained by Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol At least one selected from an epoxy (meth) acrylate resin obtained by reacting an epoxy resin with a (meth) acrylic acid, including a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, a dihydroxybenzene type epoxy resin, If necessary, it may include a thiol molecule.

The crosslinkable unit having an ethylenically unsaturated bond is preferably 0.01 to 20% by weight, 0.1 to 10% by weight, or 1 to 10% by weight in the total composition in consideration of exposure sensitivity and crosslinking efficiency.

The barrier resin composition may further include a monomer (E) or an organic solvent for viscosity adjustment. Examples of the monomer include (meth) acrylates of C ₁ -C ₂₀ , di (meth) acrylates of diols of C ₂ -C ₂₀ , tri (meth) acrylates of triols of C ₃ -C ₂₀ , and C _4- Tetra (methyl) acrylate of C ₂₀ tetraol, polyalkylene glycol di (meth) acrylate, C ₁ -C ₃₀ vinyl monomer, monofunctional (meth) acrylate containing urethane bond, urethane bond A bifunctional (meth) acrylate, a trifunctional or higher (meth) acrylate containing a urethane bond, a silane monomer containing an ethylenically unsaturated bond, a monomer containing an ethylenically unsaturated bond and containing phosphorus, an ethylenically unsaturated bond Fluorine-containing monomers may be used. The organic solvent is not particularly limited as long as it can dissolve the polymer of the present invention in organic solvents including acetate, ether, glycol, ketone, alcohol, and carbonate, usually used in the photopolymerization composition. For example, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N It may be at least one selected from solvents consisting of, N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam and the like.

The viscosity adjusting monomer or organic solvent may be in the range of 0.1 to 40% by weight, 5 to 30% by weight, or 10 to 25% by weight of the total composition, it is sufficient to control the viscosity within this range.

The barrier resin composition of the present invention may include at least one additive selected from surfactants, adhesion aids, and light stabilizers. The additive may be adjusted in kind and content according to the user's selection in the range that does not change the physical properties required by the entire photosensitive resin composition. For example, one or more additives selected from surfactants, adhesion aids, and light stabilizers may be included in the range of 0.01 to 20% by weight of the total composition.

The adhesion assistant may be, for example, a silane coupling agent having a reactive functional group including a carboxyl group, methacryloyl group, vinyl group, isocyanate group or epoxy group. Specific examples include trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyl At least one selected from trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, wherein the adhesion aid is 0.01 to 10% by weight, 0.1 to 5% by weight, or 1 to 1 in the total composition. It may be 5% by weight, it is possible to sufficiently improve the adhesion with the substrate in this range.

The surfactant may be at least one selected from the group consisting of fluorine, silicon and nonionics. The surfactant may be 0.01 to 10% by weight, 0.1 to 5% by weight, or 1 to 5% by weight of the total composition, it is possible to improve the coating properties and coating properties, uniformity and stain removal ability to the substrate in this range. .

Examples of the light stabilizer include Tinuvin 292, Tinuvin 144, Tinuvin 622LD (Shibagaiki Co., Japan), sanol LS-770, sanol LS-765, sanol LS-292, sanol LS-744 (Sankyo, Japan), and the like. . The light stabilizer may be used in the range of 0.01 to 10% by weight, 0.1 to 5% by weight, or 1 to 5% by weight of the total composition.

The photocurable blocking film may be formed using the barrier resin composition according to the exemplary embodiment of the present invention. The method of forming the photocuring barrier film is not particularly limited, and a method known in the art may be used. For example, spin coating, dip coating, roll coating, ink-jet coating, and screen coating may be used as the barrier resin composition melted and kneaded. The coating may be performed using a coating method such as flow coating, screen printing, drop casting, or the like. Thereafter, in the case of solvent-free curing (drying) step, the photocuring process may be performed directly. In the case of solvent type, the solvent may be volatilized by applying vacuum, infrared rays or heat, and then the curing process may be performed to form a photocuring barrier film. .

The exposure process is then irradiated using electromagnetic radiation in the range of 150-600 nm. Non-limiting examples of the electromagnetic radiation include microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays, electron beams, quantum rays, neutron rays, ion rays and the like. As the source of the electromagnetic radiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. In addition, the radiation dose varies depending on the composition of the composition and the film thickness of the photocuring barrier film to be formed, for example, 30 to 1000 mJ / cm 2 when using an LED lamp, preferably 100 to 1000 mJ /. May be cm 2. For example, irradiation using an excimer laser, far ultraviolet rays, ultraviolet rays, visible rays, electron beams, X-rays or g-rays (wavelength 436 nm), i-rays (365 nm wavelength), h-rays (wavelength 405 nm), or mixed rays thereof. do. Exposure can use exposure methods, such as a contact type, a proximity type, and a projection type. The photocurable dimer (B) is used as a blocking layer by photopolymerization by exposure, and the photocurable silsesquioxane resin (A) forms a blocking lamellar molecular structure in which a continuous laminated structure is formed on the blocking layer. To form.

According to one embodiment, the thickness of the photocurable blocking film formed from the above-described barrier resin composition may be selected in the range of 1 μm to 1,000 μm depending on the use. According to another embodiment, an electronic device to which the photocuring blocking film is applied is provided. Here, the photocuring blocking film may be an encapsulating material or an overcoat material. The photocuring blocking film may have the lamellar structure described above.

The photocuring barrier film may include, for example, printing inks, printing plates, encapsulants, photoresists for electronic devices, electroplating resists, etching resists, liquid and dry films, solder resists, resists for manufacturing color filters for various display applications, As a composition for encapsulating electrical and electronic components, resists for producing structures in the manufacturing process of plasma-display panels, electroluminescent displays and LCDs, compositions for manufacturing spacers for LCDs, compositions for holographic data storage (HDS), For manufacturing three-dimensional objects by stereolithography, for manufacturing magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color calibration systems, glass fiber cable coatings, screen printing stencils As recording material, holographic recording, microelectronic ash Photoresist materials for UV and visible light laser induced imaging systems, for decolorizing materials, for decolorizing materials for image recording materials, for image recording materials using microcapsules, the dielectric layer in a sequential build-up layer of a printed circuit board It can be applied to the use as a photoresist material used to form.

As a non-limiting example of the base material of the said photocuring blocking film, the board | substrate for electronic components, the thing in which predetermined wiring pattern was formed, etc. can be illustrated. Examples of the substrate include glass or plastic substrates coated with silicon, silicon nitride, silicon oxide, titanium, tantalum, palladium, titanium tungsten, copper, chromium, aluminum, AlNd, ITO, IGZO, or the like, or glass or plastic substrates. have. The substrate may be a semiconductor device substrate, a liquid crystal display (LCD) substrate, an organic light emitting diode (OLED) substrate, a solar cell substrate, a flexible display substrate, a substrate for manufacturing a touch screen, or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are intended to illustrate the present invention, but the present invention is not limited thereto.

EXAMPLE

Example 1 Synthesis of Photocurable Silsesquioxane Resin

A photocured silsesquioxane resin represented by the following Chemical Formula 1 was prepared to have a substituent shown for each synthesis example in the following table:

[Formula 1]

Synthesis Example 1 Synthesis of Photocurable Silsesquioxane Resin

[Formula 2]

Photocuring silsesquioxane resin represented by the formula (2) was prepared as follows:

80 g of tetrahydrofuran and 40 g of ultrapure water were added to a flask equipped with a stirrer and a thermometer, 0.3 g of potassium carbonate was added as a catalyst, followed by stirring at room temperature for 20 minutes to dissolve.

Then, 0.2 mol of phenyl trimethoxysilane was added and reacted for 2 hours. A mixture of 0.2 mol of trimethoxy (3- (oxirane-2-ylmethoxy) propyl) silane and 0.6 mol of 3- (triethoxysilyl) propyl methacrylate was slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 8 hours, followed by extraction of the resin with methylene chloride and distillation under reduced pressure. The photocurable silsesquioxane resin of the above-mentioned [Formula 2] (z, y, n in order from the left block of Formula 2) Molar ratio of z: y: n = 1: 1: 3). The molecular weight and polydispersity were confirmed by GPC analysis based on the product of polystyrene. As a result, the weight average molecular weight was 13,000 to 14,000 g / mol, and the polydispersity was 2.1 to 2.2.

Synthesis Example 2 Synthesis of Photocurable Silsesquioxane Resin

[Formula 3]

The photocured silsesquioxane resin represented by Formula 3 was prepared as follows:

80 g of tetrahydrofuran and 40 g of ultrapure water were added to a flask equipped with a stirrer and a thermometer, 0.3 g of potassium carbonate was added as a catalyst, followed by stirring at room temperature for 20 minutes to dissolve.

Then 0.2 mol of methyl trimethoxysilane was added and reacted for 2 hours. A mixture of 0.2 mol of phenyl triethoxysilane and 0.6 mol of styrylethyl trimethoxysilane was slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 8 hours, followed by extraction of the resin with methylene chloride and distillation under reduced pressure, wherein the target photocurable silsesquioxane resin (1y, 2y, m in order from the left block of Chemical Formula 3) Molar ratio of 1y: 2y: m = 1: 1: 3). The molecular weight and polydispersity were confirmed by GPC analysis based on the product of polystyrene. As a result, the weight average molecular weight was 12,000 to 14,000 g / mol, and the polydispersity was 2.2 to 2.4.

Synthesis Example 3 Synthesis of Photocurable Silsesquioxane Resin

[Formula 4]

The photocured silsesquioxane resin represented by Formula 4 was prepared as follows:

80 g of tetrahydrofuran and 40 g of ultrapure water were added to a flask equipped with a stirrer and a thermometer, 0.3 g of potassium carbonate was added as a catalyst, followed by stirring at room temperature for 20 minutes to dissolve.

Then 0.2 mol of methyl trimethoxysilane was added and reacted for 2 hours. A mixture of 0.2 mol of phenyl trimethoxysilane and 0.6 mol of 3-mercaptopropyl trimethoxysilane was slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 8 hours, and then the resin was extracted with methylene chloride and distilled under reduced pressure to obtain the target photocurable silsesquioxane resin (1y, 3y, x from the left block of Chemical Formula 4). Molar ratio of 1y: 3y: x = 1: 1: 3). The molecular weight and polydispersity were confirmed by GPC analysis based on the product of polystyrene. As a result, the weight average molecular weight was 15,000 to 16,000 g / mol, and the polydispersity was 2.4 to 2.5.

Synthesis Example 4-Photocuring silsesquioxane resin synthesis

[Formula 5]

Photocuring silsesquioxane resin represented by the formula (5) was prepared as follows:

80 g of tetrahydrofuran and 40 g of ultrapure water were added to a flask equipped with a stirrer and a thermometer, 0.3 g of potassium carbonate was added as a catalyst, followed by stirring at room temperature for 20 minutes to dissolve.

Then 0.2 mol of methyl trimethoxysilane was added and reacted for 2 hours. A mixture of 0.2 mol of nonafluorohexyl trimethoxysilane and 0.6 mol of 3- (triethoxysilyl) propyl methacrylate was slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropwise addition, the reaction was carried out for 8 hours, followed by extraction of the resin with methylene chloride and distillation under reduced pressure. The photocurable silsesquioxane resin of the above [Formula 5] (from the left block of Formula 5 1y: 4y: n = 1: Molar ratio of 1: 3). The molecular weight and polydispersity were confirmed by GPC analysis based on the product of polystyrene. As a result, the weight average molecular weight was 11,000 to 12,000 g / mol, and the polydispersity was 1.9 to 2.1.

<Example 1-23, Comparative Example 1-3: Blocking resin composition>

The resin compositions of Examples 1 to 23 and the barrier resin compositions of Comparative Examples 1 to 3 were prepared using the resins prepared in Synthesis Examples 1 to 4 and the resins represented by Formulas 7 or 8 described below. .

Specifically, the resin of Synthesis Examples 1 to 4, or 40 parts by weight of the resin of Comparative Examples 1 to 2, 25 parts by weight of the photocurable dimer (B) and the ethylenically unsaturated bond compound (D) are trimetholpropane triacryl. 5 parts by weight of TMPTA, 7 parts by weight of Irgacure TPO (BASF) as a photoinitiator (C), 20 parts by weight of ethyl 3-ethoxypropionate as an organic solvent, and 3 parts of adhesion promoter KBM 403 (Sinnet) at room temperature After stirring for 6 hours and filtering with a 5.0 micro pore size filter to prepare a resin composition. As the photocurable dimer (B), the compounds shown in Table 2 were used, respectively.

According to an embodiment of the present invention, as shown in the schematic diagram in Figure 1, lamellar laminated structure while connecting the photocurable dimer corresponding to the straight line notation portion of the ladder type silsesquioxane resin of the center circle notation portion Will form.

For reference, the formulas 7 to 14 in the above table are compounds represented by the following formulas:

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 7]

The compound represented by the above [Formula 7] has a weight average molecular weight of 12,000 g / mol and polydispersity of 1.8, the variable of the block from the left is 20/35/15/30, respectively.

[Formula 8]

The compound represented by the above [Formula 8] has a weight average molecular weight of 9000 g / mol and a polydispersity of 1.85, the variable of the block from the left is 20/40/40, respectively.

Meanwhile, for the comparative experiment, silsesquioxane resins containing no photocuring group were synthesized as follows:

[Formula 9]

80 g of tetrahydrofuran and 40 g of ultrapure water were added to a flask equipped with a stirrer and a thermometer, 0.3 g of potassium carbonate was added as a catalyst, followed by stirring at room temperature for 20 minutes to dissolve.

Then 0.2 mol of methyl trimethoxysilane was added and reacted for 2 hours. 0.2 mol of phenyl trimethoxysilane was slowly added dropwise to the reaction solution over 30 minutes. After completion of the dropwise reaction, the reaction was carried out for 8 hours, followed by extracting the resin with methylene chloride and distilling under reduced pressure to obtain the silsesquioxane resin without the photocuring group of the above [Formula 6] (1y, 3y from the left block of Formula 6). Molar ratio of 1y: 3y = 1: 1). The molecular weight and polydispersity were confirmed by GPC analysis based on the product of polystyrene. As a result, the weight average molecular weight was 16,000 to 17,000 g / mol, and the polydispersity was 2.2 to 2.3.

Using the barrier resin compositions of Examples 1 to 23 and Comparative Examples 1 to 3 obtained, a photocurable barrier film was prepared as follows.

That is, each of the prepared barrier resin composition is inkjetted on a substrate using an inkjet equipment on a polyimide film (thickness 75㎛), dried in an oven at 90 ° C. for 5 minutes, and then exposed to LED lamp 1000mJ / cm 2 (365nm wavelength) to 100mm. A photocuring barrier film of X 100 mm X 10 μm (width X length X thickness) was formed. The following test items were performed on the manufactured photocuring barrier film.

<Measurement method>

Oxygen permeability: The B method (isostatic method) described in JIS K7126 (2000 edition) using the oxygen transmittance | permeability measuring apparatus (OXTRAN2 / 20) made from MOCON, Inc. on condition of temperature of 23 degreeC, and 0% RH of humidity. Was measured based on Two test pieces were cut out from one sample, and each test piece was measured once, and the average value of two measured values was made into the oxygen transmittance value of the sample.

Moisture permeability : The B method (infrared sensor method) described in JIS K7129 (2000 edition) using the water vapor permeability measuring apparatus (Permatran W3 / 31) by MOCON Co., Ltd. on the conditions of 40 degreeC of temperature, and 90% RH of humidity. Was measured based on Two test pieces were cut out from one sample, and each test piece was measured once, and the average value of the two measured values was made into the water transmittance value of the sample.

Radius of curvature: The radius of curvature was measured by measuring the curvature radius from 1R to 20R using an anti-theft tester to determine whether the cured film was cracked.

Flexible durability : Flexural durability was checked for cracking of the folded surface after 100,000 folding tests were carried out at the radius of curvature 5R and 10R using a theft resistance tester.

Transparency: Transparency was measured by UV spectrum and the average transmittance of 10um in thickness and wavelength from 380nm to 800nm.

The results of oxygen permeability, moisture permeability, curvature radius, soft durability, and transparency are shown in Table 3 below.

As shown in Table 3, the resin composition according to the present invention was confirmed to have a low oxygen, water transmittance as well as excellent curvature radius and flexibility durability, transparency compared to the general cured film.

Further experiments were performed for the following additional Example 1, additional Example 2, and additional Comparative Example 1.

Additional Example 1

In the photocurable silses quoxane resin (A) of Example 1, when the content of the block (y, z) without a curing group is 5 mol% or less, it is not easy to secure properties such as chemical resistance or heat resistance of the film, It was confirmed that the film is brittle due to the degree of curing.

Additional Example 2

By using the photocurable silses quoxane resin (A) of Synthesis Examples 1 to 4 of the present embodiment, physical properties such as curvature radius and soft durability can be adjusted. For example, when the resin of Synthesis Example 2 used in the composition of Example 10 is replaced by 50% of the resin of Synthesis Example 1, it was confirmed that the soft durability is improved.

Additional Comparative Example 1

As a result of using the acrylic resin of Comparative Example 1 shows that the oxygen and moisture permeability is remarkably inferior, in order to overcome this, the composition of Comparative Example 1 was alternated three times and five times to form a multilayer to efficiently perform the performance of oxygen and moisture permeability. No security was made. From this, the acrylic resin of Comparative Example 1 could not form a lamellar three-dimensional structure even when alternating many times (multi-layer), and thus it was confirmed that the result of having no oxygen and water blocking effect.

Claims (16)

It includes a photocurable silsesquioxane resin (A), a photocurable dimer (B) and a photoinitiator (C), wherein the photocurable silsesquioxane resin (A) and the photocurable dimer (B) It contains two or more functional groups selected from the group consisting of a (meth) acryl group, a vinyl group, and a mercapto group as a short term,
The photocurable silsesquioxane resin (A) is a barrier resin composition which is a ladder resin including a structure represented by the following [Formula 1].
[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group or

R ₂ is a substituted or unsubstituted C ₁ -C ₁₂ alkyl group or a substituted or unsubstituted C ₃ -C ₁₈ hydrocarbon ring group, and R ₃ is a substituted or unsubstituted C ₃ -C ₁₀ cyclic ether containing hydrocarbon N, m and x are each an integer of 0 to 100,000 in the range of a weight average molecular weight of 1,000 to 500,000 g / mol, at least one of n, m and x is not 0, and y and z are each 0 to 100,000 to be. delete According to claim 1,
The photocurable silsesquioxane resin (A) is a ladder resin having a repeating unit represented by the following [Formula 2], a ladder resin having a repeating unit represented by the following [Formula 3], and the following [Formula 4] A barrier resin composition selected from the group consisting of a ladder resin having a repeating unit represented and a ladder resin having a repeating unit represented by the following [Formula 5]:
[Formula 2]

When the repeating unit variable is z, y, n from the left side of Formula 2, z is 0 to 40 mol%, y is 0 to 40 mol%, and n is 20 to 100 mol%.
[Formula 3]

When the variable for each repeating unit is 1y, 2y, m from the left side of Formula 3, 1y is 0 to 40 mol%, 2y is 0 to 40 mol%, and m is 20 to 100 mol%.
[Formula 4]

When the variable for each repeating unit is 1y, 3y, x from the left side of Formula 4, 1y is 0 to 40 mol%, 3y is 0 to 40 mol%, x is 20 to 100 mol%.
[Formula 5]

When the variable for each repeating unit is 1y, 4y, n from the left side of Formula 5, 1y is 0 to 40 mol%, 4y is 0 to 40 mol%, and n is 20 to 100 mol%. According to claim 1,
The photocurable dimer (B) is at least one barrier resin composition selected from the group consisting of a compound represented by the following [Formula 6], a compound represented by the following [Formula 7], and a compound represented by the following [Formula 8]. :
[Formula 6]

[Formula 7]

[Formula 8]

In Formula 6,7,8, R is hydrogen or a methyl group, R ₄ , R ₅ are independently unsubstituted or fluorine-substituted C ₁ -C ₅₀ linear or branched alkylene group, ether group or alkylene oxide Qi. According to claim 1,
The photocurable silsesquioxane resin (A) is 10 to 89.9 wt% in the total composition, the photocurable dimer (B) is 10 to 60 wt% in the total composition, and the photoinitiator (C) is in the total composition A barrier resin composition of 0.1 to 30% by weight. According to claim 1,
The photoinitiator (C) is 1-hydroxy-cyclohexylphenyl ketone, benzophenone, 2-benzyl-2- (dimethylamino) -1- (4- (4-morpholinyl) phenyl) -1-butanone , 2-methyl-1- (4-methylthio) phenyl-2- (4-morpholinyl) -1-propanone, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis ( 2,4,6-trimethylbenzoyl) phosphine oxide, benzyl-dimethylketal, isopropyl thioxanthone, ethyl (2,4,6-trimethyl benzoyl) phenyl phosphinate and phenyl (2,4,6-trimethyl benzoyl ) Phenyl phosphinate, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoylperoxide , Lauryl peroxide, t-butylperoxy pivalate, 1,1-bis (t-butylperoxy) cyclohexane, p-dimethylaminoacetophenone, 2-benzyl-2- (dimethylamino) -1- [ 4- (4-morpholinyl) phenyl] -1-butanone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, Benzoinpropyl ether, diethyl thioxanthone, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3, 4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 2- (o-chlorophenyl) -4 , 5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] -octane-1, 2-dione-2- (O-benzoyloxime), o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexa At least one selected from the group consisting of fluorophosphoro-trialkylphenylsulfonium salts, 2-mercaptobenzimidazoles, 2,2'-benzothiazolyl disulfides, chitooxime esters, alpha chitooxime esters, and mixtures thereof Barrier resin composition. According to claim 1,
The barrier resin composition comprises a crosslinkable unit (D) having at least two ethylenically unsaturated bonds, wherein the crosslinkable unit having an ethylenically unsaturated bond is selected from ethylene glycol diacrylate, ethylene glycol dimethacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate , Propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimetha Acrylate, Ta-erythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diol (Meth) to polyester prepolymers obtained by condensation of polyfunctional (meth) acrylic monomers including polyacrylates, 1,6-hexanediol dimethacrylate and cardoepoxy diacrylates, polyhydric alcohols with monobasic or polybasic acids Polyester (meth) acrylate obtained by making acrylic acid react, Polyurethane (meth) acrylate obtained by making (meth) acrylic acid react with the reaction material between compounds which have a polyol group and two isocyanate groups; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycol At least one selected from an epoxy (meth) acrylate resin obtained by reacting an epoxy resin with a (meth) acrylic acid, including a cydyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin, and a dihydroxybenzene type epoxy resin Blocking resin composition comprising in the range of 0.01 to 20% by weight. According to claim 1,
The barrier resin composition is a barrier resin composition comprising one or more additives selected from surfactants, adhesion aids, light stabilizers within the range of 0.01 to 20% by weight of the total composition. A photocurable silsesquioxane resin comprising a structure represented by the following [Formula 1], wherein a functional group selected from the group consisting of a (meth) acryl group, a vinyl group and a mercapto group at the terminal of the repeating unit of the silsesquioxane resin Ladder type outcoupling resin which contains 2-6 types,
[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group or

R ₂ is a substituted or unsubstituted C ₁ -C ₁₂ alkyl group or a substituted or unsubstituted C ₃ -C ₁₈ hydrocarbon ring group, and R ₃ is a substituted or unsubstituted C ₃ -C ₁₀ cyclic ether containing hydrocarbon N, m and x are each an integer of 0 to 100,000 in the range of a weight average molecular weight of 1,000 to 500,000 g / mol, at least one of n, m and x is not 0, and y and z are each 0 to 100,000 to be. delete The method of claim 9,
Said photocurable silsesquioxane resin is a ladder type decoupling resin in which the total amount of y and z is contained in 10 to 30 mol% of a silsesquioxane resin (A). A photocurable silsesquioxane resin (A), a photocurable dimer (B) and a photoinitiator (C) represented by the following formula (1) are melted and mixed, coated and dried on a substrate, and irradiated with light to block lamellar molecules. It comprises a step of forming a structure,
The blocking lamellar molecular structure is a photocurable dimer (B) as a blocking layer, the photocurable silsesquioxane resin (A) to form a continuous laminated structure on the surface of the barrier layer, the production of a photocurable barrier film Way:
[Formula 1]

In Formula 1, R is hydrogen or a methyl group, R ₁ is a substituted or unsubstituted C ₁ -C ₂₀ alkylene group, R ₂ is a substituted or unsubstituted C ₁ -C ₁₂ alkyl group or a substituted or unsubstituted C _{A 3} -C ₁₈ hydrocarbon ring group, R ₃ is a substituted or unsubstituted C ₃ -C ₁₀ cyclic ether containing hydrocarbon group, and n, m and x are each 0 within a weight average molecular weight of 1,000 to 500,000 g / mol An integer from 100,000 to at least one of n, m and x is not zero, and y and z are each from 0 to 100,00. The method of claim 12,
The light irradiation is a method of manufacturing a photocurable barrier film is irradiated with electromagnetic radiation in the range of 150 ~ 600 nm. An electronic device comprising a photocurable barrier film prepared from the barrier resin composition according to any one of claims 1 and 3 to 8. The method of claim 14,
The photocuring blocking film is an electronic device that is an encapsulation film material or an overcoat material. The method of claim 14,
The electronic device is a semiconductor device, a liquid crystal display (LCD), an organic light emitting device (OLED), a solar cell, a flexible display, or a touch screen display.

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