Resin composition with self-repairing function

Abstract

The invention discloses a resin composition with a self-repairing function. The resin composition comprises 20-40 parts of an acrylate reactive diluent, 5-15 parts of an acrylic acid (methyl) ester cross-linking agent containing reversible chemical bonds and 1-10 parts of a photoinitiator, the reversible chemical bond contains at least one of a ketone group, a cyano group and a disulfide bond. The acrylate reactive diluent provided by the invention is copolymerized with an acrylate cross-linking agent containing reversible chemical bonds, and the prepared film has good film-forming characteristic and optical function, and also has excellent deformation resistance and self-repairing ability.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a resin composition with self-repairing function. Technical Background

[0002] At present, in order to meet people's demand for large screens, more and more dual-screen, curved screen and folding mobile phones are appearing in the market, and the folding resistance of the screen is the most critical technical indicator of folding screen mobile phones. Most flexible folding screen mobile phones use flexible OLED screens. Since flexible OLED screens are stacked with multiple layers of different functional film layers, there are a large number of micro components and precision circuits between the layers. A simple folding, the difference in deformation recovery coefficients of different materials and the bending curvature of the inner and outer layers may cause the film layer to separate, and the film layer may slip during use. These phenomena will cause creases, fractures, wrinkles, creep and other problems on the flexible screen, affecting the service life of the screen. Therefore, it is necessary to develop materials with excellent bending resistance.

[0003] After conventional polymer materials are damaged (such as broken), the chemical bonds between the two broken surfaces are broken and cannot be reconnected, resulting in irreversible damage. In recent years, a large number of research results have found that some chemical groups such as TASN, DABBF, DABI, HABI and other materials can break chemical bonds under mechanical stimulation. After the external force is removed, these chemical groups can spontaneously collide to form chemical bonds and return to their initial state (ACS Macro Lett. 2020, 9, 1108-1113, ACS Macro Lett. 2016, 5, 1124-1127, Chemistry-A European Journal 10.1002 / chem.201800194, Macromolecules 2016, 49, 16, 5903–5911).

[0004] In view of this, the present invention is based on functional group molecules that respond to force stimulation, utilizing the fact that chemical bonds of the material break when the force is applied, and the spontaneous reaction and recovery of the functional groups after the force stimulation is removed, thereby realizing a resin composition with self-repairing function. Summary of the invention

[0005] In order to solve the above technical problems, an object is to provide a resin composition with excellent bending resistance.

[0006] The present invention provides a resin composition with a self-repairing function, comprising the following raw materials in weight fractions: 20-40 parts of a (meth)acrylate active diluent, 5-15 parts of a (meth)acrylate crosslinker containing a reversible chemical bond, and 1-10 parts of a photoinitiator;

[0007] The reversible chemical bond contains at least one of a keto group, a cyano group, and a disulfide bond.

[0008] Preferably, the (meth)acrylate crosslinking agent containing a reversible chemical bond has a structure shown in Formula I:

[0009] In Formula I, R 1 is hydrogen or methyl; L 1 C 1 -C 6 Alkyl, unsubstituted or consisting of C 1 -C 6 Alkyl, C 1 -C 6 Alkyl ether substituted phenylene, the carbon number of the carbamate bond block is C 1 -C 6 Any one of the alkylene groups;

[0010] Ar-Ar is selected from: unsubstituted or nitro, C 1 -C 6 Alkoxy, C 1 -C 6 The alcohol ether group, phenylurea group, glycidyloxy group, 2,3-diphenylsuccinonitrile group losing two symmetrical hydrogen atoms, 9,9'-bifluorene-9,9'-dinitrile group losing two symmetrical hydrogen atoms, [2,2'-benzothiophene]-3,3'(2H,2'H)-dione losing two symmetrical hydrogen atoms, [3,3'-benzofuran]-2,2'(3H,3'H)-dione losing two symmetrical hydrogen atoms, [3,3'-phenanthrofuran]-2,2'(3H,3'H)-dione losing two symmetrical hydrogen atoms, [3,3'-benzindole]-2,2'(3H,3'H)-dione losing two symmetrical hydrogen atoms, 1,1'-dithiobis[2,2,6,6-tetramethyl l-piperidine losing two symmetrical hydrogen atoms, losing two hydrogen atoms corresponding to L 1 The site of bonding.

[0011] Preferably, Ar in Formula I has the following structure:

[0012] The Ar has a structure where * represents Ar and L 1 bonding site; is a site for bridging with another Ar; X 1 is NH, O or S, X 2 is NH, O or S;

[0013] R 2 -R 8Each independently selected from: hydrogen, nitro, phenylurea, glycidoxy, C 1 -C 6 Alkyl, C 1 -C 6 Alcohol ether group, unsubstituted or composed of C 1 -C 6 Alkyl, C 1 -C 6 The phenyl group is substituted with a straight-chain alkoxy group, wherein the phenyl group is connected via a single bond or shares a pair of chemical bonds with the phenyl group to form a condensed ring structure.

[0014] Among them, the above-mentioned C1-C6 is an organic substance with a carbon atom number between 1 and 6, and the C1-C6 alkyl group can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the like.

[0015] Preferably, the (meth)acrylate crosslinking agent containing a reversible chemical bond has the following structure:

[0016]

[0017]

[0018]

[0019] Preferably, the invention further comprises 20-50 parts by weight of high-refractive-index inorganic nanoparticles, wherein the refractive index of the high-refractive-index inorganic nanoparticles is above 1.7; the high-refractive-index inorganic nanoparticles include ZrO 2 、TiO 2 、ZnS、ZnO、CeO 2 ,GeO 2 、 2 O 5 、Bi 4 Ti 3 O 2 , Nb 2 O 5 、ITO、HfO 2 SnO 2 、MoO 3 , Sb 2 O 3 , Sb 2 O 5 、Nd 2 O 3 Any one or a combination of at least two of the following.

[0020] Furthermore, the particle size of the high refractive index inorganic nanoparticles ranges from 5nm to 20nm.

[0021] If high refractive index inorganic nanoparticles are used, the acrylic ester active diluent is fluorine-free acrylic ester.

[0022] Preferably, the acrylate reactive diluent is a fluorine-free acrylate; the fluorine-free acrylate is selected from a C-containing acrylate having 1 to 6 (meth)acrylate functional groups at the end. 1 To C 20 Any one or a combination of at least two of an alkyl (meth) acrylate having 1 to 6 (meth) acrylate functional groups at the end, a C1 to C20 alkyl ether (meth) acrylate having 1 to 6 (meth) acrylate functional groups, and a (meth) acrylate containing 1 to 2 benzene rings.

[0023] Furthermore, the acrylate reactive diluent is selected from mono(meth)acrylates having C1 to C20 alkyl groups, mono(meth)acrylates having C1 to C20 alkyl ether groups, di(meth)acrylates having C1 to C20 alkylene groups, di(meth)acrylates having C1 to C20 alkylene ether groups, tri(meth)acrylates having C1 to C20 alkylene groups, tri(meth)acrylates having C1 to C20 alkylene groups, tri(meth)acrylates having C1 to C20 alkylene ether groups, tri(meth)acrylates having C1 to C20 alkylene groups, )acrylate, tri(meth)acrylate having a C1 to C20 alkylene ether group, tetra(meth)acrylate having a C1 to C20 alkylene group, tetra(meth)acrylate having a C1 to C20 alkylene ether group, penta(meth)acrylate having a C1 to C20 alkylene group, hexa(meth)acrylate having a C1 to C20 alkylene group, mono(meth)acrylate having 1 to 2 benzene rings, di(meth)acrylate having 1 to 2 benzene rings, or a combination of at least two thereof.

[0024] Further, the fluorine-free acrylate is selected from isobutyl acrylate, n-pentyl acrylate, isobutyl acrylate, isopentyl acrylate, hexyl acrylate, isooctyl acrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propylene glycol diacrylate, 1,3-propylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,12-dodecanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polybutylene glycol diacrylate, polybutylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, Glyceryl trihydroxypropyl ether triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, phenyl acrylate, phenyl methacrylate, 1,4-phenylene diacrylate, 2-phenoxyethyl methacrylate, 2-methyl-2-phenoxymethyl acrylate, 2-methyl-2-[1,1'-biphenyl]-3-ethyl-2-acrylate, 2-phenoxyethyl acrylate Acid ester, 4,4'-diphenyl diacrylate, bisphenol A dimethacrylate, bisphenol A glycerol, 2-[4-(1-methyl-1-phenylethyl)phenoxy]ethyl acrylate, 2-acrylate, (1-methylethylidene) di-4,1-phenylene ester, ethoxylated bisphenol A dimethacrylate, 2-acrylate, (1-methylethylidene) di-4,1-phenylene ester, 2-acrylate [1,1'-biphenyl]-4,4'-diylbis(oxy-2,1-ethylene) ester.

[0025] Furthermore, the invention further comprises 20-50 parts by weight of low-refractive-index inorganic nanoparticles, wherein the refractive index of the low-refractive-index inorganic nanoparticles is lower than 1.5, and the low-refractive-index inorganic nanoparticles comprise SiO 2 MgF 2 , BaF 2 Any one or a combination of at least two of the following.

[0026] Furthermore, the particle size of the low refractive index inorganic nanoparticles is in the range of 5nm-20nm.

[0027] Since the refractive index of fluorinated acrylate is relatively low, the composite material obtained by compounding with low refractive index nanoparticles is more likely to meet the low refractive index requirements. When low refractive index inorganic nanoparticles are used, the acrylate active diluent is fluorinated acrylate.

[0028] Preferably, the acrylic ester reactive diluent is a fluorinated alkyl acrylate, wherein the fluorinated alkyl acrylate is selected from fluorine-substituted C 1 To C 20 Alkyl (meth) acrylate, fluorine atom substituted with C 1 To C 20 Any one or a combination of at least two of an alkyl ether (meth) acrylate and a fluorine atom-substituted (meth) acrylate containing 1 to 2 benzene rings.

[0029] Furthermore, the fluorinated alkyl acrylate is selected from one or more combinations of trifluoroethyl acrylate, hexafluorobutyl acrylate, dodecafluoroheptyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, hexafluorobisphenol A diacrylate, perfluorodiethylene glycol diacrylate, perfluoropropane-1,3-diylbis(3,3-difluoro-2-methylacrylate), perfluoropropane dimethacrylate, 2-(perfluorobutyl)ethyl methacrylate, and 4-tridecafluorooctyl-benzoate-acrylate.

[0030] Preferably, the composition further comprises any one of an adhesion promoter, a surfactant, a defoaming agent, a stabilizer, and a solvent, or a combination of at least two of them.

[0031] Furthermore, when the resin composition of the present invention contains an adhesion promoter, the amount of the adhesion promoter added is 0.1-1 parts by weight; the adhesion promoter is a silane compound, and the adhesion promoter used in the present invention includes but is not limited to: one or more of bis[3-(triethoxysilyl)propyl]amine, 3-(isomethacryloyloxy)propyltrimethoxysilane, and (3-mercaptopropyl)trimethoxysilane.

[0032] Furthermore, when the resin composition of the present invention contains a surfactant, the amount of the surfactant added is 0.1-1 parts by weight; the surfactant can use a silicone or fluorine-based surfactant, as a specific example, there can be listed: one or more of the following: 3M commercial products FC-4430, FC-4432, DuPont commercial products FS-10, FS-22, FS-61, BYK-345, BYK-346, BYK-348, BYK-349, German BYK commercial products, German Tego commercial product TEGO-4100, etc.

[0033] Furthermore, when the resin composition of the present invention contains a defoamer, the amount of the defoamer added is 0.1-1 parts by weight; the defoamer is selected from: polysiloxane defoamers, mineral oil defoamers, polyether modified silicone defoamers, silicone defoamers, and the defoamers used in the present invention include but are not limited to: Shin-Etsu Chemical Co., Ltd.'s Shin-Etsu KS-66 defoamer and BYK307, BYK051, BYK052, BYK053, and BYK066N defoamers of BYK Additives (Shanghai) Co., Ltd.

[0034] Furthermore, when the resin composition of the present invention contains a stabilizer, the stabilizer is added in an amount of 0.01-0.05 parts by weight. The stabilizer includes, but is not limited to, one of butylated hydroxytoluene and p-hydroxyanisole or a mixture thereof.

[0035] Furthermore, when the resin composition of the present invention contains a solvent, the amount of the solvent added is 40-60 parts by weight;

[0036] Further, the solvent is an organic solvent selected from one of esters, alcohols, ethers, ketones, benzenes or a mixture thereof. The ester solvent is selected from one of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono-butyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and cyclohexanol acetate;

[0037] The alcohol is selected from one or more of methanol, ethanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and triethylene glycol;

[0038] The ethers are selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;

[0039] Ketones are selected from one or more of acetone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone and methyl hexyl ketone;

[0040] The benzene is selected from: one or more of toluene and xylene.

[0041] Furthermore, the solvent is one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and diethylene glycol monoethyl ether acetate, or a mixture of any multiple thereof.

[0042] Furthermore, the preferred technical solution of the present invention is solvent-free.

[0043] Preferably, the photoinitiator is a conventional initiator with a photocuring function, which may include, for example, any one of α-hydroxyketone initiators, benzoin initiators, acylphosphine oxide initiators, acetophenone initiators, and morpholinyl ketone initiators, or a combination of at least two thereof.

[0044] Further, the α-hydroxyketone initiator is selected from: 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-hydroxyethoxy)phenyl-1-propanone, polymerized [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], difunctional α-hydroxyketone, and one or more of 4,4'-bis(diethylamino)benzophenone.

[0045] Furthermore, the benzoin initiator is selected from any one of benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin dimethyl ether, and benzoin diethyl ether, or a combination of at least two thereof.

[0046] Furthermore, the acylphosphine oxide initiator is selected from: any one or a combination of at least two of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl (2,4,6-trimethylbenzoyl)phenylphosphine ester.

[0047] Furthermore, the acetophenone photoinitiator is selected from any one of 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone, or a combination of at least two thereof.

[0048] On the other hand, the resin composition with self-repairing function provided by the present invention can be used to prepare an optical material layer in an OLED, MiniLED or Micro LED display device.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The resin composition with self-repairing function provided by the present invention is formed by copolymerization of an acrylate cross-linking agent containing a reversible chemical bond and an acrylic reactive diluent without a reversible chemical bond. When the film made of the film is deformed, due to the breaking and healing effect of the reversible chemical bonds in the highly cross-linked mesh film structure, the film can have a good anti-deformation ability, thereby avoiding the film material from being broken due to folding, or when the film has a certain degree of physical damage (such as cracks), the broken chemical bonds are bonded again, thereby allowing the film material to be automatically repaired. It can also be further doped with high-refractive inorganic nanoparticles, low-refractive inorganic nanoparticles, aromatic (methyl) acrylates or fluorine-containing (methyl) acrylates, so that it is suitable for use as a high-refractive optical functional layer, a low-refractive optical functional layer or an encapsulation layer in a display device, reducing the power consumption of the display, and improving the stability of device use and the yield rate of the production line. DETAILED DESCRIPTION

[0051] The embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific conditions are specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0052] In the embodiment, the inorganic nanoparticles are added in the form of being mixed with a commercially available dispersant: the dispersing solvent is commercially available PGMEA (propylene glycol methyl ether acetate), and the wt% of the inorganic nanoparticles is 40-60%. In this embodiment, the mass fraction of the inorganic nanoparticles is 50%.

[0053] Synthesis Example 1:

[0054]

[0055] Add 2,3-bis(4-hydroxyphenyl)-2,3-bis(-4-methoxyphenyl)succinonitrile (47.65g, 0.1mol) to a 500mL three-necked round-bottom flask equipped with a thermometer, a magnetic stirrer and a reflux condenser and dissolve it in 250ml of dichloromethane. Then add triethylamine (10.12g 0.1mol). Add a mixed solution of 50ml of dichloromethane containing acryloyl chloride (18.11g, 0.2mol) dropwise under an ice-water bath, add 4-dimethylaminopyridine (12.22g, 0.1mol) as a catalyst and react for 24h. After the reaction is complete. After washing with ice water and diluted HCl, add sodium bicarbonate aqueous solution to wash and adjust to neutrality, and finally wash with saturated NaCl aqueous solution, separate the liquids, dry the organic phase with anhydrous MgSO4, filter and spin dry the solvent, and finally recrystallize with anhydrous ethanol to obtain compound A1. The molecular weight was 584.71 detected by mass spectrometry, which was confirmed to be the target product.

[0056] Synthesis Example 2:

[0057]

[0058] Add 2,2'-bis(hydroxymethyl)-9H,9'-[9,9'-difluorene]-9,9'-dicarbonitrile (44.05g, 0.1mol) and dissolve it in 250ml of dichloromethane to a 500mL three-necked round-bottom flask equipped with a thermometer, a magnetic stirrer and a reflux condenser. Then add triethylamine (10.12g 0.1mol). Add a mixed solution of 50ml of dichloromethane containing 2-(chlorocarbonyl)amino)ethyl acrylate (35.52g, 0.2mol) dropwise under an ice-water bath and react for 8h. After the reaction is complete. After washing with ice water and diluted HCl, add sodium bicarbonate aqueous solution to wash and adjust to neutrality, and finally wash with saturated NaCl aqueous solution, separate the liquids, dry the organic phase with anhydrous MgSO4, filter and spin dry the solvent, and finally recrystallize with anhydrous ethanol to obtain compound A6. The molecular weight was 722.51 detected by mass spectrometry, which was confirmed to be the target product.

[0059] It should be noted that, in the present invention, other acrylate crosslinking agents containing reversible chemical bonds other than those in Synthesis Example 1 and Synthesis Example 2 can be obtained by the same reaction principle and reaction operation.

[0060] Embodiment 1:

[0061] The acrylate (meth) crosslinking agent containing a reversible chemical bond is selected from the structural formula A1.

[0062] 35 parts by weight of isobutyl acrylate and 10 parts by weight of an acrylate crosslinking agent are added into a reaction kettle and stirred evenly, and then 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole are successively added into the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0063] Embodiment 2:

[0064] The (methyl) acrylate crosslinking agent containing a reversible chemical bond is selected from the structural formula A2.

[0065] 20 parts by weight of isobutyl acrylate, 5 parts by weight of butyl terephthalate, and 5 parts by weight of an acrylate crosslinking agent are put into a reaction kettle and stirred evenly, and then 1 part by weight of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.1 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.1 parts by weight of BYK053, 0.1 parts by weight of FC-4430, and 0.01 parts by weight of p-hydroxyanisole are successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0066] Embodiment 3:

[0067] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A3.

[0068] 30 parts by weight of isobutyl acrylate, 10 parts by weight of biphenylmethanol acrylate, and 15 parts by weight of an acrylate crosslinking agent are put into a reaction kettle and stirred evenly, and then 10 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1 part by weight of bis[3-(triethoxysilyl)propyl]amine, 1 part by weight of BYK053, 0.1 parts by weight of FC-4430, and 0.05 parts by weight of butylated hydroxytoluene are successively added into the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0069] Embodiment 4:

[0070] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A5.

[0071] 35 parts by weight of isobutyl acrylate, 10 parts by weight of acrylate crosslinking agent, 25 parts by weight of 20 nm GeO 2After being put into the reaction kettle and stirred evenly, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0072] Embodiment 5:

[0073] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A6.

[0074] 35 parts by weight of isobutyl acrylate, 10 parts by weight of acrylate crosslinking agent, 25 parts by weight of 5nmSb 2 O 3 After being put into the reaction kettle and stirred evenly, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0075] Embodiment 6:

[0076] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A7.

[0077] 25 parts by weight of pentaerythritol tetraacrylate, 12 parts by weight of acrylate crosslinking agent, 25 parts by weight of 10 nm Sb 2 O 3 After being put into the reaction kettle and stirred evenly, 3 parts by weight of 2,2-dimethoxyacetophenone, 0.3 parts by weight of (3-mercaptopropyl)trimethoxysilane, 0.3 parts by weight of BYK060N, 0.2 parts by weight of BYK-346, and 0.02 parts by weight of p-hydroxyanisole are successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0078] Embodiment 7:

[0079] The (methyl) acrylate crosslinking agent containing a reversible chemical bond is selected from the structural formula A8.

[0080] 28 parts by weight of bisphenol A dimethacrylate, 12 parts by weight of acrylate crosslinking agent, 35 parts by weight of 20 nm ZrO 2After being put into the reaction kettle and stirred evenly, 7 parts by weight of 2,2-dimethoxyacetophenone, 0.4 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.6 parts by weight of BYK088, 0.5 parts by weight of BYK-346, and 0.04 parts by weight of p-hydroxyanisole are successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0081] Embodiment 8:

[0082] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A11.

[0083] 18 parts by weight of isobutyl acrylate, 20 parts by weight of bisphenol A dimethacrylate, 15 parts by weight of acrylate crosslinker, and 30 parts by weight of 10 nm ZrO2 are put into a reactor and stirred evenly, and then 4 parts by weight of benzoin isopropyl ether, 0.4 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.6 parts by weight of BYK088, 0.4 parts by weight of FS-10, and 0.04 parts by weight of butylated hydroxytoluene are successively added into the reactor and stirred for 1 hour to prepare the resin composition.

[0084] Embodiment 9:

[0085] The acrylate crosslinking agent containing a reversible chemical bond is selected from the structural formula A12.

[0086] 35 parts by weight of hexyl acrylate, 6 parts by weight of acrylate crosslinking agent, 45 parts by weight of 20 nm ZrO 2 After being put into the reaction kettle and stirred evenly, 7 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.4 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.6 parts by weight of BYK060N, 0.8 parts by weight of FS-10 and 0.02 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0087] Embodiment 10:

[0088] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A14.

[0089] 42 parts by weight of hexyl acrylate, 6 parts by weight of methyl acrylate crosslinking agent, 50 parts by weight of 20 nm ZrO 2 After being put into the reaction kettle and stirred evenly, 3 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.2 parts by weight of BYK060N, 0.8 parts by weight of FS-10 and 0.04 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0090] Example 11: (low fold)

[0091] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A15.

[0092] 35 parts by weight of isobutyl acrylate, 10 parts by weight of acrylate crosslinking agent, 25 parts by weight of 20 nm SiO 2 After being put into the reaction kettle and stirred evenly, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0093] Comparative Example 1:

[0094] 25 parts by weight of pentaerythritol tetraacrylate, 25 parts by weight of 10 nm Sb 2 O 3 After being put into the reaction kettle and stirred evenly, 3 parts by weight of 2,2-dimethoxyacetophenone, 0.3 parts by weight of (3-mercaptopropyl)trimethoxysilane, 0.3 parts by weight of BYK060N, 0.2 parts by weight of BYK-346, and 0.02 parts by weight of p-hydroxyanisole are successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0095] Comparative Example 2:

[0096] 35 parts by weight of isobutyl acrylate, 10 parts by weight of tetraarylsuccinonitrile, 25 parts by weight of 20 nm GeO 2 After being put into the reaction kettle and stirred evenly, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0097] Comparative Example 3:

[0098] 35 parts by weight of hexyl acrylate, 6 parts by weight of aromatic benzofuran copolymer (3,3'-diphenyl-[3,3'-dibenzofuran]-2,2'(3H,3'H)-dione), 45 parts by weight of 20 nm ZrO 2After being put into the reaction kettle and stirred evenly, 7 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.4 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.6 parts by weight of BYK060N, 0.8 parts by weight of FS-10 and 0.02 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0099] Comparative Example 4:

[0100] The acrylate (methyl) ester crosslinking agent containing a reversible chemical bond is selected from the structural formula A1.

[0101] 10 parts by weight of an acrylate crosslinking agent, 25 parts by weight of a 20 nm GeO 2 After being put into the reaction kettle and stirred evenly, 5 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 0.5 parts by weight of bis[3-(triethoxysilyl)propyl]amine, 0.5 parts by weight of BYK053, 0.5 parts by weight of FC-4430 and 0.03 parts by weight of p-hydroxyanisole were successively added to the reaction kettle and stirred for 1 hour to prepare the resin composition.

[0102] Performance testing:

[0103] The resin compositions prepared in Examples 1 to 11 and Comparative Examples 1-4 were numbered 1-15, and their viscosities were measured by a viscometer, and then 5um was coated on a quartz substrate using inkjet printing technology. After the substrate was dried in a vacuum oven for 30 minutes, it was placed in a UV curing machine and irradiated with an intensity of about 2000mJ / cm2 to form a refractive film. The refractive index was measured by an Abbe refractometer, the elongation at break was measured by a tensile machine, and the width of the healed scratch of the high refractive film at room temperature after the same initial scratch width was healed for 4 hours was measured by an optical microscope. The self-healing efficiency was calculated according to the formula (healed scratch width / initial scratch width). The test results are shown in Table 1 below:

[0104] Table 1

[0105]

[0106]

[0107] It can be seen from Table 1 above that the resin composition provided by the present invention is prepared by using an acrylate cross-linking agent containing a reversible chemical bond, inorganic nanoparticles, a photoinitiator, a solvent and other functional additives. On the one hand, in the inorganic nanoparticle doping system, the resin composition is effectively endowed with the high (low) refractive index characteristics and light transmittance possessed by the inorganic nanoparticles; on the other hand, the combined polymer of the acrylate cross-linking agent with a reversible chemical bond has better optical functions, tensile toughness and self-repairing ability than the resin compositions of Comparative Examples 1-3, and is a composition with excellent comprehensive performance, and has excellent application prospects in display devices such as OLED, Mini LED, and Micro LED.

[0108] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection of the present invention.

Claims

1. A resin composition having a self-repairing function, characterized in that: The raw materials include the following weight fractions: 20-40 parts of (meth)acrylate active diluent, 5-15 parts of (meth)acrylate crosslinking agent containing reversible chemical bonds and 1-10 parts of photoinitiator; The reversible chemical bond contains at least one of a keto group, a cyano group, and a disulfide bond.

2. A resin composition with self-repairing function according to claim 1, characterized in that: The (meth)acrylate crosslinking agent containing a reversible chemical bond has a structure shown in Formula I: In formula I, R1 is hydrogen or methyl; L1 is a C1-C6 alkyl group, a phenylene group which is unsubstituted or substituted by a C1-C6 alkyl group or a C1-C6 alkyl ether group, and the carbon number of the carbamate bond block is any one of C1-C6 alkylene groups; Ar-Ar is selected from: unsubstituted or substituted nitro, C1-C6 alkoxy, C1-C6 alcohol ether, phenylurea, glycidyloxy 2,3-diphenylsuccinonitrile group losing two symmetrical hydrogen atoms, 9,9'-bifluorene-9,9'-dinitrile group losing two symmetrical hydrogen atoms, [2,2'-benzothiophene]-3,3'(2H,2'H)-dione losing two symmetrical hydrogen atoms, [3,3' -benzofuran]-2,2'(3H,3'H)-dione, [3,3'-phenanthrofuran]-2,2'(3H,3'H)-dione which loses two symmetric hydrogen atoms, [3,3'-benzindole]-2,2'(3H,3'H)-dione which loses two symmetric hydrogen atoms, 1,1'-dithiobis[2,2,6,6-tetramethyl l-piperidine which loses two symmetric hydrogen atoms, the loss of two hydrogen atoms corresponds to the bonding site with L1.

3. A resin composition with self-repairing function according to claim 2, characterized in that: In formula I, Ar has the following structure: In the structure of Ar, * is the bonding site between Ar and L1; is a site for bridging with another Ar; X1 is NH, O or S, and X2 is NH, O or S; R2-R8 are each independently selected from: hydrogen, nitro, phenylurea, glycidoxy, C1-C6 alkyl, C1-C6 alcohol ether, phenyl which is unsubstituted or substituted by C1-C6 alkyl or C1-C6 straight-chain alkoxy, wherein the phenyl is connected by a single bond or shares a pair of chemical bonds with the phenyl to form a condensed ring structure.

4. A resin composition with self-repairing function according to claim 3, characterized in that: The (meth)acrylate crosslinking agent containing a reversible chemical bond has the following structure:

5. The resin composition with self-repairing function according to claim 1, characterized in that: It also includes 20-50 weight parts of high-refractive-index inorganic nanoparticles, wherein the refractive index of the high-refractive-index inorganic nanoparticles is above 1.7; the high-refractive-index inorganic nanoparticles include any one of ZrO2, TiO2, ZnS, ZnO, CeO2, GeO2, Ta2O5, Bi4Ti3O2, Nb2O5, ITO, HfO2, SnO2, MoO3, Sb2O3, Sb2O5, and Nd2O3, or a combination of at least two of them.

6. The resin composition with self-repairing function according to claim 5, characterized in that: The acrylate reactive diluent is a fluorine-free acrylate; the fluorine-free acrylate is selected from a C1 to C2 acrylate having 1 to 6 (meth)acrylate functional groups at the end. 20 Any one or a combination of at least two of an alkyl (meth) acrylate having 1 to 6 (meth) acrylate functional groups at the end, a C1 to C20 alkyl ether (meth) acrylate having 1 to 6 (meth) acrylate functional groups, and a (meth) acrylate containing 1 to 2 benzene rings.

7. The resin composition with self-repairing function according to claim 1, characterized in that: The invention also comprises 20-50 parts by weight of low-refractive-index inorganic nanoparticles, wherein the refractive index of the low-refractive-index inorganic nanoparticles is lower than 1.5, and the low-refractive-index inorganic nanoparticles comprise any one of SiO2, MgF2, and BaF2, or a combination of at least two of them.

8. The resin composition with self-repairing function according to claim 7, characterized in that: The acrylic ester reactive diluent is a fluorinated alkyl acrylate, wherein the fluorinated alkyl acrylate is selected from a fluorine-substituted alkyl acrylate having C1 to C 20 Alkyl (meth) acrylate, fluorine atom substituted with C1 to C 20 Any one or a combination of at least two of an alkyl ether (meth) acrylate and a fluorine atom-substituted (meth) acrylate containing 1 to 2 benzene rings.

9. The resin composition with self-repairing function according to claim 1, characterized in that: It also includes any one of an adhesion promoter, a surfactant, a defoaming agent, a stabilizer, and a solvent, or a combination of at least two of them.

10. The resin composition with self-repairing function according to claim 1, characterized in that: The photoinitiator is any one of α-hydroxy ketone initiators, benzoin initiators, acylphosphine oxide initiators, acetophenone initiators, morpholinyl ketone initiators, and oxime ester photoinitiators, or a combination of at least two of them.

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