阅读说明：本技术 组合物及含有其的封装薄膜和制备方法以及电子器件 (Composition, packaging film containing composition, preparation method of packaging film and electronic device ) 是由 王群 宋鑫 宣玉凤 冯铭竹 刘稀蒙 刘墨宁 刘贤豪 于 2020-05-22 设计创作，主要内容包括：本发明提出了组合物、含有其的封装薄膜及其制备方法和电子器件,所述组合物包括：第一组分,所述第一组分选自第一烷氧基硅烷化合物或其低聚物,所述第一烷氧基硅烷化合物中具有至少一个与硅原子相连的环氧基；第二组分,所述第二组分选自第二烷氧基硅烷化合物或其低聚物；第三组分,所述第三组分选自至少一种潜在酸固化剂；以及第四组分,所述第四组分包括溶剂。本发明的组合物形成的有机层具有较好的阻隔性、平整性和粘接性,可与无机层形成多层阻隔叠堆的封装薄膜,整体上提高封装薄膜的性能。并且,该组合物稳定性强,保质期长,应用前景好。(The invention provides a composition, an encapsulation film containing the composition, a preparation method of the encapsulation film and an electronic device, wherein the composition comprises the following components: a first component selected from a first alkoxysilane compound having at least one epoxy group bonded to a silicon atom therein or an oligomer thereof; a second component selected from a second alkoxysilane compound or oligomer thereof; a third component selected from at least one latent acid curing agent; and a fourth component comprising a solvent. The organic layer formed by the composition has better barrier property, smoothness and adhesion, can form a multilayer barrier stacked packaging film together with an inorganic layer, and improves the performance of the packaging film on the whole. In addition, the composition has strong stability, long shelf life and good application prospect.)

1. A composition, comprising:

a first component selected from a first alkoxysilane compound having at least one epoxy group bonded to a silicon atom therein or an oligomer thereof;

a second component selected from a second alkoxysilane compound or oligomer thereof;

a third component selected from at least one latent acid curing agent; and

a fourth component comprising a solvent.

2. The composition of claim 1, wherein the first alkoxysilane compound has a structure represented by formula (1):

wherein Y is selected from C_1～6Alkylene radical, C_6～20Arylene, wherein alkylene or arylene may optionally be substituted by ether linkages, acyl groups orWherein n is an integer from 1 to 20; r₁Is selected from oxo C_1～6Cycloalkyl or epoxycyclohexylalkyl;

R₂and R₄Are independently selected fromFrom C_1～6Alkyl radical, C_2～6Alkenyl radical, C_3～6Alkynyl, C_6～20Aryl, -Y-R₁OR-OR₃；

R₃Is selected from C_1～6An alkylene group.

3. The composition of claim 1, wherein the second alkoxysilane compound has at least three hydrolytic condensation sites therein;

optionally, the second component comprises at least one of tetramethoxysilane, oligomeric tetramethoxysilane, tetraethoxysilane, oligomeric tetraalkoxysilane, methyltrimethoxysilane, and oligomeric methyltrimethoxysilane;

optionally, a hydrolyzable site-OR in the composition₃The mole ratio of the silicon atoms to the silicon atoms is not more than 1.5 and not less than 0.3;

optionally, the third component is selected from a photoacid curing agent and/or a thermal acid curing agent;

optionally, the photoacid curing agent comprises at least one of: 4,4' -dimethyldiphenyliodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylthiotetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium arsenate, diphenyliodonium trifluoromethanesulfonate, triphenylthiotetrafluoroborate, triphenylsulfonium bromide and tri-p-tolylsulfonium hexafluorophosphate;

optionally, the thermal acid curing agent comprises at least one of: 2,4,4, 6-tetrabromocyclohexadienone, dinonylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid trifluoride, p-toluenesulfonic acid, benzoin tosylate, phenyl triflate, 2-nitrobenzyl tosylate, benzylic halogenated aromatic compounds, monoalkyl and dialkyl acid phosphates, monophenyl and diphenyl acid phosphates and alkylphenyl acid phosphates;

optionally, the fourth component further comprises a wetting dispersant;

optionally, the composition further comprises: a fifth component comprising an alkoxide, halide, or complex of at least one hydrolyzable metal;

optionally, the metal is selected from aluminum, titanium or zirconium;

optionally, the alkoxide, halide or complex of a hydrolysable metal is selected from the group consisting of alumina, aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-isopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetoacetate, aluminum triacetylacetonate, aluminum nitrate, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra (2-ethylhexanol), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate, zirconium tetra-n-propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate.

4. The composition according to claim 1, wherein the mass ratio of the first component to the second component is (1.0-100): 1;

optionally, the third component is contained in an amount of 1 to 30 parts by weight, the fourth component is contained in an amount of 0.1 to 1000 parts by weight, and the fifth component is contained in an amount of 0 to 30 parts by weight, based on 100 parts by weight of the total mass of the first component and the second component.

5. An encapsulation film, comprising: an organic layer and an inorganic layer alternately stacked;

at least one of the organic layers is formed from the composition of any one of claims 1 to 4.

6. The encapsulation film according to claim 5, wherein the surface roughness of the organic layer formed from the composition is not more than 10 nm;

optionally, the thickness of the organic layer is 0.1-20 μm, and the thickness of the inorganic layer is 5-500 nm;

optionally, the material of the inorganic layer is selected from at least one of an oxide, nitride or oxynitride of Al, Si, Zr, Ti, Hf, Ta, In, Sn, Zn.

7. A method for producing the encapsulating film according to claim 5 or 6, comprising:

the composition is applied to an inorganic layer and cured to form an organic layer on the inorganic layer.

8. The method of claim 7, wherein the curing comprises:

heating and drying the inorganic layer applied with the composition, and then carrying out photocuring treatment; or directly subjecting the inorganic layer applied with the composition to a heat curing treatment to form an organic layer on the inorganic layer;

optionally, the conditions of the photocuring treatment are as follows: the irradiation wavelength is 250-400 nm, and the energy is 300-3000 MJ/cm²；

Optionally, the conditions of the thermal curing process are as follows: the heating temperature is 50-200 ℃, and the heating time is 0.5-600 min.

9. The method of claim 8, wherein prior to applying the composition to the inorganic layer, the composition is subjected to a controlled hydrolytic condensation, and wherein the controlled hydrolytic condensation results in a first component and a second component having hydrolyzable sites-OR ™₃The mole ratio of the silicon atoms to the silicon atoms is not more than 1.5 and not less than 0.3;

optionally, the organic layer has a surface roughness of no greater than 10 nm.

10. An electronic device, comprising:

a substrate;

an electronic element formed on the substrate; and

an encapsulating film as claimed in claim 5 or 6, which encapsulates the entire surface of the electronic component.

Technical Field

The invention relates to the field of materials. In particular, the invention relates to a composition, an encapsulation film containing the composition, a preparation method and an electronic device.

Background

Many active materials in the field of flexible electronics are sensitive to water and oxygen and must be encapsulated with water and oxygen barrier materials, which otherwise can seriously affect the service life of the device. Although the traditional packaging material glass can obtain higher barrier property, the traditional packaging material glass has the defects of being heavy, fragile and unbendable, and the application range of the traditional packaging material glass is severely limited. Current alternatives include: 1) the active functional layer is attached and packaged by adopting a flexible barrier substrate; 2) and packaging the functional material by adopting an online film deposition mode. The key barrier layer in the above scheme is typically an inorganic oxide, nitride or oxynitride prepared by chemical vapor or physical vapor deposition, which is well known in the art. These inorganic layers alone present challenges such as: when the thickness is increased to a certain degree, the barrier property is not increased or even deteriorated, which is mainly due to the fact that some defects in the inorganic layer can grow throughout; the film forming process environment of inorganic materials is too harsh for many functional materials in flexible electronic devices, and the device can be damaged when the online thin film packaging is directly carried out.

The problem has been shown to be solved to a greater extent by a multilayer stacking route "inorganic/organic/inorganic/organic". The introduction of the organic layer prevents defect through growth in the inorganic layer while providing a flat surface for subsequent inorganic layer deposition.

However, currently, organic layer materials suitable for use in multilayer stacks remain to be investigated.

Disclosure of Invention

The present invention aims to solve at least to some extent at least one of the technical problems of the prior art.

It should be noted that the present invention has been completed based on the following findings of the inventors:

the inventors have found that when the organic layer material is pure organic, when the organic layer material and the inorganic layer are alternately deposited, the difference between the thermo-mechanical properties of the two layers is large, and thus the risk of interlayer adhesion failure is likely to occur.

In view of the above, the inventors tried to form an organic layer using an organic material and an inorganic material together, specifically, an organic silane resin as a host material. Further, the inventors found that linking of silicon atoms in alkoxysilanes with different groups significantly affects the properties of organic materials, such as leveling, barrier properties, storage properties, etc. Further, the inventors have found, through intensive studies, that when an alkoxysilane compound having at least one epoxy group bonded to a silicon atom or an oligomer thereof (first alkoxysilane compound) is used in combination with another alkoxysilane compound or an oligomer thereof (second alkoxysilane compound), the two silane compounds may be subjected to controlled hydrolytic condensation either individually or after being mixed. Under the catalytic action of a potential acid curing agent, the epoxy groups are subjected to ring-opening polymerization to form an organic network, and meanwhile, residual siloxane in a molecular chain can be further hydrolyzed and is subjected to condensation reaction with adjacent-OH. Therefore, the formed three-dimensional network structure not only enables the organic layer to have excellent leveling performance, but also enables the inorganic layer to have excellent bonding performance, has good blocking effect, can effectively block moisture from entering in a high-temperature or high-humidity environment, and has good application prospect.

To this end, in one aspect of the invention, a composition is provided. According to an embodiment of the invention, the composition comprises: a first component selected from a first alkoxysilane compound having at least one epoxy group bonded to a silicon atom therein or an oligomer thereof; a second component selected from a second alkoxysilane compound or oligomer thereof; a third component selected from at least one latent acid curing agent; and a fourth component comprising a solvent.

In the composition according to the embodiment of the present invention, an alkoxysilane compound having at least one epoxy group bonded to a silicon atom or an oligomer thereof (first alkoxysilane compound) is used in combination with another alkoxysilane compound or an oligomer thereof (second alkoxysilane compound), and the two silane compounds may be subjected to controlled hydrolytic condensation either individually or after being mixed. Under the catalytic action of a potential acid curing agent, the epoxy groups are subjected to ring-opening polymerization to form an organic network, and meanwhile, residual siloxane in a molecular chain can be further hydrolyzed and is subjected to condensation reaction with adjacent-OH. Therefore, the formed three-dimensional network structure not only enables the formed organic layer to have excellent leveling performance, but also enables the formed organic layer to have excellent bonding performance on the inorganic layer, and meanwhile, the three-dimensional network structure has an obvious effect of improving the barrier performance of the inorganic layer. In addition, the composition has high stability and long shelf life. Thus, the organic layer formed by the composition according to the embodiment of the invention has better barrier property, flatness and adhesion, and can form a packaging film of a multilayer barrier stack together with the inorganic layer, so that the performance of the packaging film is improved as a whole. In addition, the composition has strong stability, long shelf life and good application prospect.

According to an embodiment of the invention, the compound may also have the following additional technical features:

according to an embodiment of the present invention, the first alkoxysilane compound has a structure represented by formula (1),

a group; r₂And R₄Each independently selected from C_1～6Alkyl radical, C_2～6Alkenyl radical, C_3～6Alkynyl, C_6～20Aryl, -Y-R₁OR-OR₃；R₃Is selected from C_1～6An alkylene group.

According to an embodiment of the present invention, the second alkoxysilane compound has at least three hydrolytic condensation sites therein.

According to an embodiment of the present invention, the second component includes at least one of tetramethoxysilane, oligomeric tetramethoxysilane, tetraethoxysilane, oligomeric tetraalkoxysilane, methyltrimethoxysilane, and oligomeric methyltrimethoxysilane.

According to an embodiment of the invention, the composition has a hydrolysable site-OR₃The molar ratio to silicon atoms is not more than 1.5 and not less than 0.3.

According to an embodiment of the invention, the third component is selected from a photoacid curing agent and/or a thermal acid curing agent.

According to an embodiment of the present invention, the photoacid curing agent comprises at least one of: 4,4' -dimethyldiphenyliodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylthiotetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium arsenate, diphenyliodonium trifluoromethanesulfonate, triphenylthiotetrafluoroborate, triphenylsulfonium bromide and tri-p-tolylsulfonium hexafluorophosphate.

According to an embodiment of the present invention, the thermal acid curing agent comprises at least one of: 2,4,4, 6-tetrabromocyclohexadienone, dinonylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzoin tosylate, phenyl triflate, 2-nitrobenzyl tosylate, benzylic halogenated aromatics, mono-and dialkyl acid phosphates, mono-and diphenyl acid phosphates, and alkylphenyl acid phosphates.

According to an embodiment of the invention, said fourth component further comprises a wetting dispersant.

According to an embodiment of the invention, the composition further comprises: a fifth component comprising an alkoxide, halide, or complex of at least one hydrolyzable metal.

According to an embodiment of the invention, the metal is selected from aluminium, titanium or zirconium.

According to an embodiment of the invention, the alkoxide, halide or complex of a hydrolysable metal is selected from the group consisting of aluminium oxide, aluminium triethoxide, aluminium tri-n-propoxide, aluminium tri-isopropoxide, aluminium tri-n-butoxide, aluminium tri-tert-butoxide, aluminium triacetate, aluminium acetoacetate, aluminium triacetylacetonate, aluminium nitrate, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra (2-ethylhexanol), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate, zirconium tetra-n-propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate.

According to the embodiment of the invention, the mass ratio of the first component to the second component is (1.0-100): 1.

according to an embodiment of the present invention, the third component is contained in an amount of 1 to 30 parts by weight, the fourth component is contained in an amount of 0.1 to 1000 parts by weight, and the fifth component is contained in an amount of 0 to 30 parts by weight, based on 100 parts by weight of the total mass of the first component and the second component.

In another aspect of the invention, an encapsulation film is provided. According to an embodiment of the present invention, the encapsulation film includes: an organic layer and an inorganic layer alternately stacked; at least one of the organic layers is formed from the composition described above. As described above, the organic layer formed by the composition according to the embodiment of the present invention has good barrier property, flatness and adhesion, and can form a multilayer barrier stacked packaging film with an inorganic layer, so as to improve the performance of the packaging film as a whole, and make the packaging film have good barrier property and adhesion, and be suitable for large-scale application.

According to an embodiment of the present invention, the surface roughness of the organic layer formed from the composition is not greater than 10 nm.

According to the embodiment of the invention, the thickness of the organic layer is 0.1-20 μm, and the thickness of the inorganic layer is 5-500 nm.

According to an embodiment of the present invention, the material of the inorganic layer is selected from at least one of an oxide, a nitride or an oxynitride of Al, Si, Zr, Ti, Hf, Ta, In, Sn, Zn.

In yet another aspect of the present invention, the present invention provides a method of preparing the aforementioned encapsulation film. According to an embodiment of the invention, the method comprises: the composition is applied to an inorganic layer and cured to form an organic layer on the inorganic layer. Therefore, the packaging film obtained by the method provided by the embodiment of the invention has excellent barrier property, flatness and compactness and overall performance, and is suitable for large-scale application.

According to an embodiment of the invention, the curing comprises; heating and drying the inorganic layer applied with the composition, and then carrying out photocuring treatment; or directly subjecting the inorganic layer applied with the composition to a heat curing process to form an organic layer on the inorganic layer.

According to an embodiment of the present invention, the conditions of the photo-curing process are as follows: the irradiation wavelength is 250-400 nm, and the energy is 300-3000 MJ/cm²。

According to an embodiment of the present invention, the conditions of the heat curing process are as follows: the heating temperature is 50-200 ℃, and the heating time is 0.5-600 min.

According to an embodiment of the invention, before the composition is applied on the inorganic layer, the composition is previously subjected to a controlled hydrolytic condensation, the hydrolyzable sites-OR-of the first and second components after said controlled hydrolytic condensation₃The molar ratio to silicon atoms is not more than 1.5 and not less than 0.3.

According to an embodiment of the present invention, a surface roughness of the organic layer is not more than 10 nm.

In yet another aspect of the present invention, an electronic device is presented. According to an embodiment of the present invention, the electronic device includes: a substrate; an electronic element formed on the substrate; and the packaging film is used for packaging the whole surface of the electronic element. Therefore, the electronic device provided by the embodiment of the invention has strong stability and good weather resistance.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

FIG. 1 shows a schematic diagram of an encapsulation film structure according to an embodiment of the invention;

fig. 2 shows a schematic structural view of an electronic device according to an embodiment of the invention.

Detailed Description

The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention.

It should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Further, in the description of the present invention, "a plurality" means two or more unless otherwise specified.

The present invention proposes a composition, an encapsulation film, and a method of preparing the encapsulation film and an electronic device, which will be described in detail, respectively, below.

Composition comprising a metal oxide and a metal oxide

In one aspect of the invention, a composition is provided. According to an embodiment of the invention, the composition comprises: a first component selected from a first alkoxysilane compound having at least one epoxy group bonded to a silicon atom or an oligomer thereof; a second component selected from a second alkoxysilane compound or oligomer thereof; a third component selected from at least one latent acid curing agent; and a fourth component comprising a solvent.

In the composition according to the embodiment of the present invention, an alkoxysilane compound having at least one epoxy group bonded to a silicon atom or an oligomer thereof (first alkoxysilane compound) is used in combination with another alkoxysilane compound or an oligomer thereof (second alkoxysilane compound), and the two silane compounds may be subjected to controlled hydrolytic condensation either individually or after being mixed. Under the catalytic action of a potential acid curing agent, the epoxy groups are subjected to ring-opening polymerization to form an organic network, and meanwhile, residual siloxane in a molecular chain can be further hydrolyzed and is subjected to condensation reaction with adjacent-OH. Therefore, the formed three-dimensional network structure not only enables the formed organic layer to have excellent leveling performance, but also enables the formed organic layer to have excellent bonding performance on the inorganic layer, and meanwhile, the three-dimensional network structure has an obvious effect of improving the barrier performance of the inorganic layer. In addition, the composition has high stability and long shelf life. Thus, the organic layer formed by the composition according to the embodiment of the invention has better barrier property, flatness and adhesion, and can form a packaging film of a multilayer barrier stack together with the inorganic layer, so that the performance of the packaging film is improved as a whole. In addition, the composition has strong stability, long shelf life and good application prospect.

In the alkoxysilane compound of the present invention, the mode of bonding the epoxy group to the silicon atom is not particularly limited, and the epoxy group may be directly bonded to the silicon atom or bonded to the silicon atom through another group to form an a-B-Si structure, where a is an epoxy group and B is another group.

According to an embodiment of the present invention, the alkoxysilane compound has a structure represented by formula (1):

wherein Y is selected from C_1～6Alkylene radical, C_6～20Arylene, wherein alkylene or arylene may optionally be substituted by ether linkages, acyl groups orWherein n is an integer from 1 to 20; r₁Selected from oxocyclopropyl, oxocyclobutyl or epoxyCyclohexane radical

R₂And R₄Each independently selected from C_1～6Alkyl radical, C_2～6Alkenyl radical, C_3～6Alkynyl, C_6～20Aryl, -Y-R₁OR-OR₃；

R₃Is selected from C_1～6An alkylene group.

According to an embodiment of the invention, the first component is selected from a compound or oligomer thereof selected from one of the following:

2- (3, 4-epoxycyclohexyl) ethyl-trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl-triethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl-tripropoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl-triphenoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl-diethoxymethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl-dimethoxyethoxysilane, (glycidoxypropyl) -trimethoxysilane, (glycidoxypropyl) -triethoxysilane, (glycidoxypropyl) -tripropoxysilane, (glycidoxypropyl) -diethoxymethoxysilane, di-n-ethoxysilane, di-, (glycidoxypropyl) -dimethoxyethoxysilane.

The above compounds or oligomers thereof can be carried out by controlled hydrolytic condensation, preferably by means of basic catalysts, such as: ammonia water, tetramethylhydroxylamine, tetraethylhydroxylamine, sodium hydroxide, potassium hydroxide, barium hydroxide, strongly basic ion exchange resins, and the like. The degree of hydrolysis and condensation reaction can be realized by adjusting reaction temperature, solvent and the like, and the degree of hydrolysis can be monitored by HNMR, Raman spectrum and the like.

According to an embodiment of the present invention, the second alkoxysilane compound has at least three hydrolytic condensation sites therein. Thereby, the alkoxysilane compound or oligomer thereof can be made to form a three-dimensional network structure with the first component, and the denseness of the coating can be improved. In some preferred embodiments, the second component comprises at least one of tetramethoxysilane, oligomeric tetramethoxysilane, tetraethoxysilane, oligomeric tetraalkoxysilane, methyltrimethoxysilane, and oligomeric methyltrimethoxysilane.

According to embodiments of the present invention, the first and second components of the composition may be subjected to controlled hydrolytic condensation separately or may be mixed and subjected to controlled co-hydrolytic condensation. Integral hydrolyzable sites-OR in the first and second components after hydrolytic condensation₃The molar ratio to silicon atoms is not more than 1.5 and not less than 0.3. The inventors have found that-OR is present in the composition₃The mole ratio of the silicon atoms to the organic layer reflects the pre-reaction degree of the composition and the degree of subsequent reaction, further influences the crosslinking degree, leveling property and the like of the coating, and finally influences the barrier property, the smoothness, the bonding property with the inorganic layer and the like of the formed organic layer. The inventor finds that when the ratio is larger than 1.5, the obtained organic layer has more defects, so that the barrier property is poor; when the ratio is less than 0.3, the leveling property of the coating is poor in the adhesion property of the organic and inorganic layers.

According to an embodiment of the invention, the third component is selected from a photoacid curing agent and/or a thermal acid curing agent. The latent acid curing agent does not chemically react with other components in the composition under conventional storage conditions, and only after being excited by light or/and heat, the latent acid curing agent releases hydrogen ions to catalyze the ring-opening reaction of the alkoxy silicon bonded epoxy functional group. Also, some acid is generated during this process, promoting further condensation crosslinking of the hydrolyzable sites in the first and second components.

According to embodiments of the present invention, the photoacid curing agent may be a cationic photocurable agent comprising at least one of: 4,4' -dimethyldiphenyliodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenylthiotetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium arsenate, diphenyliodonium trifluoromethanesulfonate, triphenylthiotetrafluoroborate, triphenylsulfonium bromide and tri-p-tolylsulfonium hexafluorophosphate. Specifically, the curing conditions were: the irradiation wavelength is 250-400 nm, and the energy is 300-3000 MJ/cm²。

According to an embodiment of the invention, the thermal acid curing agent comprises at least one of: 2,4,4, 6-tetrabromocyclohexadienone, dinonylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzoin tosylate, phenyl triflate, 2-nitrobenzyl tosylate, benzylic halogenated aromatics, mono-and dialkyl acid phosphates, mono-and diphenyl acid phosphates, and alkylphenyl acid phosphates. Specifically, the curing temperature is 50-200 ℃, and the curing time is 0.5-600 min.

According to an embodiment of the invention, the fourth component further comprises a wetting dispersant. The addition of the wetting dispersant is beneficial to the smooth spreading of the coating liquid on the coating substrate and the improvement of the appearance of the coating. According to a particular embodiment of the invention, the wetting and dispersing agent is selected from at least one of the following: BKY-W985, BYK-W969, BYK-W996, BYK-W9010, BYK-310, BYK-W980, BYK-W966, BYK-W940 and BYK-9076.

The type of the solvent is not strictly limited in the present invention, as long as the components can be dissolved to form a uniform mixed solution, and the solvent can be flexibly selected according to actual conditions. According to an embodiment of the invention, the solvent is selected from at least one of the following: methanol, ethanol, propanol, isopropanol, acetone, butanone, methyl propyl ketone, ethylene glycol monoethyl ether, ethyl acetate, butyl acetate, etc.

According to an embodiment of the invention, the composition further comprises: a fifth component comprising an alkoxide, halide, or complex of at least one hydrolyzable metal. The addition of the fifth component can participate in the construction of the three-dimensional network, and plays a role in adjusting the density and the strength of the network.

According to an embodiment of the invention, the metal is selected from aluminium, titanium or zirconium. In some embodiments, the alkoxide, halide, or complex of a hydrolyzable metal is selected from the group consisting of aluminum oxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-isopropoxide, aluminum tri-n-butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetoacetate, aluminum triacetylacetonate, aluminum nitrate, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetra (2-ethylhexanol), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate, zirconium tetra-n-propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate.

According to the embodiment of the invention, the mass ratio of the first component to the second component is (1.0-100): 1. the proportion is obtained by a large number of experiments, and if the addition amount of the first component is too much, the formed organic layer has low barrier property; if the addition amount of the second component is too large, phase separation is easily caused during curing, so that the surface flatness of the organic layer is affected, and the toughness of the film layer is low.

According to an embodiment of the present invention, the third component is contained in an amount of 1 to 30 parts by weight, the fourth component is contained in an amount of 0.1 to 1000 parts by weight (preferably 0.1 to 120 parts by weight), and the fifth component is contained in an amount of 0 to 30 parts by weight, based on 100 parts by weight of the total mass of the first component and the second component. The inventor obtains the preferable proportion through a large amount of experiments, so that the curing speed is high, and the performance of the formed organic layer is good. For example, if the amount of the third component is too small, the curing rate is low, which affects the production efficiency; if the addition amount of the third component is too large, on one hand, the production cost is increased, and on the other hand, the density of the three-dimensional network is influenced by residual components in the curing agent, so that the barrier property is reduced.

Packaging film

In another aspect of the invention, an encapsulation film is provided. According to an embodiment of the present invention, referring to fig. 1, the encapsulation film includes: organic layers 10 and inorganic layers 20 are alternately stacked, and at least one organic layer 10 is formed of the composition as described above. Therefore, as mentioned above, the organic layer formed by the composition according to the embodiment of the invention has better barrier property, flatness and adhesion, and can form a multilayer barrier stacked packaging film with the inorganic layer, so that the performance of the packaging film is improved as a whole, and the packaging film has better barrier property and adhesion, and is suitable for large-scale application.

According to an embodiment of the present invention, the surface roughness of the organic layer formed from the composition is not greater than 10 nm. Therefore, the formed organic layer has good flatness and is beneficial to forming an inorganic layer subsequently.

According to the embodiment of the invention, the thickness of the organic layer is 0.1-20 μm. Therefore, the method is beneficial to the effective coverage of the inorganic layer and has good flatness. Meanwhile, the stress of the film layer can be reduced, and the water vapor is prevented from permeating from the side surface.

According to the embodiment of the invention, the thickness of the inorganic layer is 5-500 nm. Therefore, continuous film forming is facilitated, the formed film system is high in stability, and the phenomenon of cracking and layering under the subsequent aging condition is avoided.

According to an embodiment of the present invention, the material of the inorganic layer is selected from at least one of an oxide, a nitride or an oxynitride of Al, Si, Zr, Ti, Hf, Ta, In, Sn, Zn. Thereby, excellent properties are imparted to the encapsulating film.

It will be appreciated by those skilled in the art that the features and advantages described above for the composition apply equally to the encapsulating film and will not be described in further detail herein.

Method for preparing packaging film

In yet another aspect of the present invention, the present invention provides a method of preparing the aforementioned encapsulation film. According to an embodiment of the invention, the method comprises: the composition is applied to the inorganic layer and cured to form an organic layer on the inorganic layer. Therefore, the packaging film obtained by the method provided by the embodiment of the invention has good barrier property, smoothness and compactness, and excellent overall performance, and is suitable for large-scale application.

It is to be noted that the manner of applying the composition according to the present invention is not strictly limited, and conventional gravure coating, doctor blade, slot coating, ink jet printing, spin coating, etc. may be used for the deposition of the organic layer.

According to an embodiment of the invention, curing comprises; heating and drying the inorganic layer applied with the composition, and then carrying out photocuring treatment; or directly subjecting the inorganic layer applied with the composition to a heat curing treatment to form an organic layer on the inorganic layer. The solvent in the composition is removed by heating and drying treatment, and then the first component and the second component are crosslinked fully by photocuring and/or thermocuring treatment, and meanwhile, the epoxy group is subjected to ring-opening reaction under the action of the latent acid curing agent and is further crosslinked with the second component, so that a three-dimensional network structure is constructed, and the organic layer is endowed with better properties such as barrier property, smoothness and the like.

According to an embodiment of the present invention, the conditions of the photo-curing process are as follows: the irradiation wavelength is 250-400 nm, and the energy is 300-3000 MJ/cm²(ii) a The conditions of the heat curing treatment were as follows: the heating temperature is 50-200 ℃, and the heating time is 0.5-600 min. The inventor finds that under the curing conditions, the first component and the second component can generate a crosslinking reaction, and release hydrogen ions after the latent acid curing agent is subjected to light or heat excitation, so that the ring-opening reaction of the epoxy functional groups is catalyzed, the formation of a three-dimensional network structure is further promoted, and the adhesion and the barrier property are improved.

According to an embodiment of the invention, before the composition is applied on the inorganic layer, the composition is subjected beforehand to a controlled hydrolytic condensation, the hydrolyzable sites-OR-of the first and second components after said controlled hydrolytic condensation₃The molar ratio to silicon atoms is not more than 1.5 and not less than 0.3. It should be noted that the hydrolysis treatment mainly involves the first component and the second component, and the inventors found that the degree of prehydrolysis of the first component and the second component affects the barrier property, flatness, adhesion, etc. of the organic layer, and further, by monitoring-OR in the first component and the second component during hydrolysis₃When the molar ratio of the organic layer to the silicon atom is within the range of 0.3-1.5, the finally formed organic layer has the characteristics of good barrier property, smoothness, adhesive property and the like.

In the present invention, the method of performing controlled hydrolytic condensation on the composition in advance is not limited strictly, and the first component and the second component may be subjected to controlled hydrolytic condensation separately, or may be subjected to controlled cohydrolytic condensation after mixing the first component and the second component, and may be selected flexibly according to actual conditions.

According to embodiments of the present invention, the composition on the dried inorganic layer is more easily spread and leveled such that the surface roughness of the organic layer is no greater than 10nm (preferably no greater than 5 nm). Therefore, the inorganic layer is formed on the surface of the substrate in a subsequent process.

It will be understood by those skilled in the art that the features and advantages described above for the encapsulation film apply equally to the method of preparing the encapsulation film and will not be described in detail here.

Electronic device

In yet another aspect of the present invention, an electronic device is presented. According to an embodiment of the present invention, referring to fig. 2, an electronic device includes: a substrate 100; an organic electronic element 200, the organic electronic element 200 being formed on the substrate 100; and the encapsulation film 300 described above, the encapsulation film 300 encapsulates the entire surface of the organic electronic element 200. Therefore, the organic electronic device provided by the embodiment of the invention has strong stability and good weather resistance.

It will be appreciated by those skilled in the art that the features and advantages described above for the encapsulation film apply equally to the method of the electronic device and will not be described in detail here.

The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Preparing a barrier substrate: a100 nm SiOx layer was deposited by PECVD on 100 μm PET with a water permeability of 40mg/m²day^-1。