Optical adhesive composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of materials, and particularly relates to an optical adhesive composition as well as a preparation method and application thereof. In the optical adhesive composition, a component A comprises 10 wt%-60 wt% of acrylic resin A, 20 wt%-70 wt% of a first inorganic filler and 0 wt%-20 wt% of a functional aid; the component B comprises 20 wt%-50 wt% of acrylate B, 30 wt%-70 wt% of a second inorganic filler, 1 wt%-25 wt% of a curing agent and 0 wt%-3 wt% of a functional aid; the acrylic resin A at least contains alkyl (meth) acrylate, alkyl ether (meth) acrylate or aryl (meth) acrylate containing one or more reactive groups, and the reactive groups are selected from any one or more of hydroxyl, epoxy or carboxyl. After the optical adhesive composition disclosed by the invention is completely cured and reacted, an adhesive layer has the properties of compact crosslinking density, good water-oxygen barrier property, high temperature resistance and the like.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and specifically relates to an optical adhesive composition and a preparation method and application thereof. Background Art

[0002] Optical glue is a special adhesive used to bond transparent optical components (such as lenses, etc.). It is colorless and transparent, has a light transmittance of more than 90%, has good bonding strength, can be cured at room temperature or medium temperature, and has small curing shrinkage.

[0003] UV heating dual curing glue is often used in various fields. Compared with traditional pure UV curing glue or pure heat curing glue, it has excellent characteristics such as fast curing, multiple curing methods, and wide adaptability. In addition, it has many advantages such as low heat curing temperature and energy saving and environmental protection. However, the current UV heating dual curing glue has problems such as high shrinkage rate, poor water resistance after curing, slow curing speed, high curing temperature requirements, and low strength after curing. It cannot meet the structural bonding requirements of new materials such as glass, metal, LCP, and PET. Therefore, the present invention proposes an optical adhesive composition to solve this problem. Summary of the invention

[0004] In order to solve the deficiencies of the prior art, the present invention provides an optical adhesive composition and a preparation method and application thereof.

[0005] The technical solution provided by the present invention is as follows:

[0006] An optical adhesive composition comprises two components, component A and component B, wherein component A comprises 10wt% to 60wt% of acrylic resin A, 20wt% to 70wt% of a first inorganic filler, and 0wt% to 20wt% of a functional additive; component B comprises 20wt% to 50wt% of acrylate B, 30wt% to 70wt% of a second inorganic filler, 1wt% to 25wt% of a curing agent, and 0wt% to 3wt% of a functional additive;

[0007] The acrylic resin A at least comprises an alkyl (meth)acrylate, an alkyl (meth)acrylate ether or an aryl (meth)acrylate containing one or more reactive groups, wherein the reactive groups are selected from any one or more of hydroxyl, epoxy or carboxyl groups; and the curing agent at least comprises a photocuring agent.

[0008] In the above technical solution:

[0009] The curing agent is set in the component B. By separating the component A from the component B, the resin in the components A and B can be prevented from solidifying, so that the high-fold dual-curing adhesive has good fluidity and is easy to use in construction.

[0010] Furthermore, the component A also contains 20wt%-70wt% of epoxy resin. The curing agent also includes a thermal curing agent.

[0011] Based on the above technical solution:

[0012] The (meth) alkyl acrylate containing one or more reactive groups has both an unsaturated double bond that can react with acrylate B and a reactive group that can react with epoxy resin. The epoxy group can be thermally cured with the reactive group, and the double bonds can be photocured, thereby achieving dual curing. The overall crosslinking density of the composition is increased by dual curing, and the impact strength, high temperature resistance, refractive index, light transmittance and other properties of the optical adhesive after the optical adhesive composition is cured are significantly improved;

[0013] Separating the epoxy resin and the curing agent into two components, A and B, prevents the epoxy resin and the first acrylate from being cured at room temperature, so that the composition has good fluidity. At the same time, it is beneficial to improve the dispersibility of the inorganic filler, thereby improving the optical properties of the cured adhesive layer, such as the refractive index.

[0014] Specifically, the alicyclic group includes a C1-20 alkyl chain having a C3-15 cycloalkyl group. In the technical scheme of the present application, one or more H on the C1-20 alkyl chain having a C3-15 cycloalkyl group can be replaced by a C2-5 heterocycle, examples of which include: epoxy group, etc.; the C2-5 heterocycle can be co-bonded with the C3-15 cycloalkyl group, examples of which include: epoxycyclohexyl.

[0015] Specifically, the aromatic group includes C6-30 aromatic groups and aromatic groups having two or more benzene rings, wherein the multiple benzene rings are connected by single bonds, heteroatoms or C1-5 alkyl groups; examples include bisphenol A, bisphenol F, bisphenol S, and the like.

[0016] That is, in the technical solution of the present application, the epoxy resin can be selected from any one or more combinations of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, novolac epoxy resin, glycidyl ester epoxy resin, and glycidyl ether epoxy resin.

[0017] The epoxy resin is selected from any one or more combinations of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, novolac epoxy resin, and epoxy glycidyl ester.

[0018] The bisphenol A epoxy resin includes one or more of E-44 epoxy resin, E-51 epoxy resin, E-32 epoxy resin, E-35 epoxy resin, E-54 epoxy resin, E128 epoxy resin, E20 epoxy resin, and E10 epoxy resin.

[0019] The bisphenol F type epoxy resin includes one or more of epoxy resin DER354, epoxy resin DER354LV, EXA-830CRP, epoxy resin 828EL, 862, YDF170, and YDF175.

[0020] The bisphenol S epoxy resin includes one or more of S33 bisphenol S epoxy resin, 185S bisphenol S epoxy resin, and 300SS bisphenol S epoxy resin.

[0021] The above-mentioned bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin are only examples. Similarly, the biphenyl epoxy resin, novolac epoxy resin, and epoxy glycidyl ester described in this application can all be selected from commercially available models.

[0022] Specifically, the acrylate B comprises alkyl (meth)acrylate, alkyl ether (meth)acrylate or aryl (meth)acrylate, and the acrylic resin A and the acrylate B are the same as or different from each other.

[0023] Further, in the present application: the (meth) acrylate alkyl ester is a C1-C 20 Alkyl mono(meth)acrylate, or having C1-C 20 Alkylene multifunctional (meth)acrylates;

[0024] The (meth) acrylic acid alkyl ether ester is a C1-C 20 Alkyl mono(meth)acrylate, or, C1-C 20 Alkylene multifunctional (meth)acrylates;

[0025] The (meth)acrylate is a C6-C 30 Aromatic mono(meth)acrylate, or C6-C 30 A multifunctional (meth)acrylate of an aromatic group, wherein the aromatic group is directly connected to the (meth)acrylate by a single bond, or is connected via a C1-C6 alkyl group, or is connected via a C1-C6 alkyl ether group.

[0026] Preferably, the acrylate B contains at least two or more phenyl groups or one or more epoxy groups.

[0027] Preferably, the types of acrylate A are one, two or three.

[0028] Preferably, the type of acrylate B is one or two.

[0029] Specifically, the photocuring agent can be selected from photoinitiators conventionally used in photocurable resin compositions, such as benzoin photoinitiators, ketone photoinitiators, phosphine oxide photoinitiators, peroxide photoinitiators, and oxime ester photoinitiators.

[0030] Specifically, the thermal curing agent can be a thermal curing initiator conventionally used for thermal curing resin compositions, such as an amine-based curing agent, an acid anhydride-based thermal curing agent, an imidazole-based thermal curing agent, an acid anhydride-based curing agent, and the like.

[0031] Amine curing agents include, for example, N,N-dimethylbenzylamine, triethylenetetramine, diethyltoluenediamine, 1,3-cyclohexanedimethylamine, dapsone, isophoronediamine, 4,4'-bis-sec-butylaminodiphenylmethane, ammonium-blocked Lewis acid salts, and the like.

[0032] The heat curing agent in the present application preferably uses an amine curing agent. Based on this scheme, the epoxy groups in the epoxy resin and acrylic resin A react with the heat curing agent amine to form a large number of hydroxyl groups, which form hydrogen bonds with the hydroxyl groups on the surface of the glass substrate. In addition, the epoxy groups can react with the hydroxyl groups on the glass substrate to form chemical bonds, which can firmly connect the glass substrate and the resin and improve the bonding strength of the interface.

[0033] Preferably, the first inorganic filler and the second inorganic filler are selected from one or more combinations of organically modified or unmodified metal oxides and silicon dioxide. The average particle size of the inorganic filler in the technical solution of the present application is 10-50 nm. Examples of metal oxides include, but are not limited to, metal oxides composed of one or two metal elements of zirconium, titanium, germanium, niobium, zinc, hafnium, tantalum, bismuth, molybdenum, tin, indium, antimony, cerium, neodymium, hafnium, and tantalum with high refractive index, and specifically include: zirconium dioxide, titanium dioxide, etc.

[0034] Organic modification is a well-known and commonly used technical means such as conventional silane coupling agent modification. The organic modified zirconium dioxide and the like specifically selected in this application are commercially available.

[0035] The functional additives include one or a combination of defoaming agent, dispersant, leveling agent, coupling agent and thixotropic agent, and the silane coupling agent contains at least one functional group of hydroxyl, epoxy or amino.

[0036] The hydroxyl, epoxy or amino functional group in the silane coupling agent can be located on any carbon of the silane coupling agent.

[0037] Based on this scheme, the silane coupling agent contains silicon-oxygen-carbon bonds, which can react with the hydroxyl groups on the surface of the glass substrate to form silicon-oxygen-carbon chemical bonds, which can firmly connect the silane molecules to the surface of the glass substrate. The epoxy group and acryl group at the other end can react with the epoxy group and acryl group in the resin, thereby firmly connecting to the resin, thereby improving the adhesion between the resin and the glass substrate.

[0038] In the present application, the silane coupling agent is specifically selected as: a silane coupling agent having a hydroxyl group, an epoxy group or an amino group at one end and a siloxane group at the other end. Examples include but are not limited to: 3-aminopropyl diisopropylethoxysilane, y-aminopropyl triethoxysilane, N-(β-aminoethyl)-y-aminopropyl trimethyl (ethyl)oxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, etc.

[0039] In the embodiment of the present invention, a surfactant is added, and the specific options include but are not limited to: polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane containing multiple acrylate functional groups, hydroxyl-containing polyether-modified polydimethylsiloxane, and acryloxy-modified silane polymer.

[0040] In the second aspect, the present application provides an adhesive layer, wherein component A and component B are put into a reaction kettle at a weight ratio of (1-1.5):1, stirred and mixed evenly, pre-cured under ultraviolet light, and then cured at 100-130°C to obtain an adhesive layer.

[0041] The technical solution of the present application is also applicable to the curing method of UV and heat curing at the same time, or heat curing first and then UV curing. However, the method of UV curing first and then heat curing is more preferred, and the obtained cured adhesive is more completely cured and has better optical and mechanical properties.

[0042] In the present application, acrylic resin monomers having reactive functional groups are selected in component A, epoxy resins and acrylate monomers in component B are mixed. Due to the presence of reactive groups, the acrylic resin monomers having reactive functional groups can undergo cross-linking reactions with the epoxy resin and the acrylate in component B at the same time under the action of a thermal curing agent and a light curing agent, so that after curing, the resin in component A and the acrylic resin in component B will form a polymerized entity bonded by strong chemical bonds, thereby improving the thermal stability, mechanical strength and optical properties of the material.

[0043] The acrylic ester component in the components A and B is selected from acrylic esters with smaller chain segments, and the degree of intermolecular entanglement after mixing is smaller. Therefore, the two components A and B have good fluidity and a lower thermal expansion coefficient after mixing;

[0044] After components A and B are mixed, UV curing is first used. The acrylate with reactive groups in component A first reacts with acrylate to obtain an initial cross-linking density. After the thermal curing is completely reacted, the adhesive layer has a dense cross-linking density and has good water and oxygen barrier properties, high temperature resistance and other properties. DETAILED DESCRIPTION

[0045] The principles and features of the present invention are described below. The examples are only used to explain the present invention and are not intended to limit the scope of the present invention. If no specific conditions are specified in the examples, the conditions are carried out according to conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be obtained commercially.

[0046] Embodiment 1:

[0047] S1: 20 parts by weight of glyceryl methacrylate, 50 parts by weight of diglycidyl adipate, 25 parts by weight of organically modified zirconium dioxide and 2 parts by weight of 3-glycidyloxypropyltrimethoxysilane were added into a reaction kettle and stirred at a temperature of 45° C., a stirring speed of 1500 rpm and a stirring time of 4 hours to obtain component A.

[0048] S2: 30 parts by weight of o-phenylphenoxyethyl acrylate, 50 parts by weight of organically modified zirconium dioxide, 10 parts by weight of diethyltoluenediamine, 5 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1 part by weight of polyether modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0049] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0050] Embodiment 2:

[0051] S1: 20 parts by weight of glyceryl methacrylate, 50 parts by weight of bisphenol A epoxy resin (E-03 type), 15 parts by weight of 4-biphenylmethanol acrylate, 25 parts by weight of organically modified zirconium dioxide and 2 parts by weight of 3-glycidyloxypropyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0052] S2: 30 parts by weight of o-phenylphenoxyethyl acrylate, 50 parts by weight of organically modified zirconium dioxide, 10 parts by weight of diethyltoluenediamine, 5 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1 part by weight of polyether modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0053] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0054] Embodiment 3:

[0055] S1: 20 parts by weight of 2-acrylic acid, 2-hydroxy-2-phenylethyl ester, 50 parts by weight of bisphenol A epoxy resin (E-03 type), 15 parts by weight of 4-biphenylmethanol acrylate, 25 parts by weight of organically modified zirconium dioxide and 2 parts by weight of 3-glycidyloxypropyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0056] S2: 30 parts by weight of o-phenylphenoxyethyl acrylate, 50 parts by weight of organically modified zirconium dioxide, 10 parts by weight of diethyltoluenediamine, 5 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1 part by weight of polyether modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0057] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0058] Embodiment 4:

[0059] S1: 20 parts by weight of 2-acrylic acid, 2-hydroxy-2-phenylethyl ester, 50 parts by weight of 4,5-epoxytetrahydrophthalic acid diglycidyl ester, 15 parts by weight of 4-biphenylmethanol acrylate, 25 parts by weight of organically modified zirconium dioxide and 2 parts by weight of 3-glycidyloxypropyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0060] S2: 30 parts by weight of o-phenylphenoxyethyl acrylate, 50 parts by weight of organically modified zirconium dioxide, 10 parts by weight of diethyltoluenediamine, 5 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1 part by weight of polyether modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0061] Product preparation: Component A and component B are added into a reaction kettle at a ratio of 1.2:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0062] Embodiment 5:

[0063] S1: 18 parts by weight of 9,9-bis[4-(2-hydroxy-3-acryloxypropoxy)phenyl]fluorene, 52 parts by weight of 1,2-cyclohexanediol diglycidyl ether, 10 parts by weight of o-phenylphenoxyethyl acrylate, 20 parts by weight of organically modified zirconium dioxide and 1 part by weight of vinyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0064] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0065] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0066] Embodiment 6:

[0067] S1: 18 parts by weight of 9,9-bis[4-(2-hydroxy-3-acryloxypropoxy)phenyl]fluorene, 52 parts by weight of bisphenol A epoxy resin, 10 parts by weight of o-phenylphenoxyethyl acrylate, 20 parts by weight of organically modified zirconium dioxide and 1 part by weight of vinyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0068] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0069] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0070] Embodiment 7:

[0071] S1: 18 parts by weight of bisphenol A diglycidyl ether diacrylate, 52 parts by weight of 1,2-cyclohexanediol diglycidyl ether, 10 parts by weight of o-phenylphenoxyethyl acrylate, 20 parts by weight of organically modified zirconium dioxide and 1 part by weight of vinyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0072] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0073] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0074] Embodiment 8:

[0075] S1: 15 parts by weight of glycidyl methacrylate, 65 parts by weight of bisphenol F diglycidyl ether, 20 parts by weight of organically modified titanium dioxide and 1 part by weight of 3-(2,3-epoxypropoxy)propyltrimethoxysilane are added into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C. The stirring speed is 1500 rpm and the stirring time is 4 hours to obtain component A.

[0076] S2: 40 parts by weight of bisetherfluorene acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0077] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0078] Embodiment 9:

[0079] S1: 15 parts by weight of 3,4-epoxycyclohexyl methacrylate, 65 parts by weight of bisphenol F diglycidyl ether, 20 parts by weight of organically modified titanium dioxide and 1 part by weight of 3-(2,3-epoxypropoxy)propyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0080] S2: 40 parts by weight of bisetherfluorene acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0081] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0082] Embodiment 10:

[0083] S1: 25 parts by weight of mono[2-[(2-methyl-acryloyl)oxy]ethyl] succinate, 40 parts by weight of pentaerythritol glycidyl ether, 15 parts by weight of 3-phenoxybenzyl acrylate, 18 parts by weight of organically modified zirconium dioxide and 5 parts by weight of y-aminopropyltriethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0084] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 50 parts by weight of organically modified zirconium dioxide, 15 parts by weight of diethyltoluenediamine, 7 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1.5 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0085] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0086] Embodiment 11:

[0087] S1: 25 parts by weight of mono[2-[(2-methyl-acryloyl)oxy]ethyl] succinate, 40 parts by weight of diglycidyl phthalate, 15 parts by weight of 3-phenoxybenzyl acrylate, 18 parts by weight of organically modified zirconium dioxide and 5 parts by weight of y-aminopropyltriethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0088] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 50 parts by weight of organically modified zirconium dioxide, 15 parts by weight of diethyltoluenediamine, 7 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1.5 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0089] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0090] Embodiment 12:

[0091] S1: 25 parts by weight of mono[2-[(2-methyl-acryloyl)oxy]ethyl] succinate, 40 parts by weight of diglycidyl phthalate, 15 parts by weight of 3-phenoxybenzyl acrylate, 18 parts by weight of organically modified zirconium dioxide and 5 parts by weight of silane coupling agent KH-580 are put into a reactor and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0092] S2: 30 parts by weight of glycidyl methacrylate, 50 parts by weight of organically modified zirconium dioxide, 15 parts by weight of diethyltoluenediamine, 7 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 1.5 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0093] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0094] Embodiment 13:

[0095] S1: 18 parts by weight of 9,9-bis[4-(2-hydroxy-3-acryloxypropoxy)phenyl]fluorene, 52 parts by weight of 2-propenoic acid, (1-methylethylidene)bis-4,1-phenylene ester, 10 parts by weight of o-phenylphenoxyethyl acrylate, 20 parts by weight of organically modified zirconium dioxide and 1 part by weight of vinyltrimethoxysilane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component A.

[0096] S2: 30 parts by weight of 4-biphenylmethanol acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0097] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0098] Embodiment 14:

[0099] S1: 15 parts by weight of ethyl methacrylate, 65 parts by weight of bisphenol F diglycidyl ether, 20 parts by weight of organically modified titanium dioxide and 1 part by weight of 3-(2,3-epoxypropoxy)propyltrimethoxysilane were added into a reaction kettle and stirred. The temperature was controlled between 25°C and 50°C, the stirring speed was 1500 rpm, and the stirring time was 4 hours to obtain component A.

[0100] S2: 40 parts by weight of bisetherfluorene acrylate, 55 parts by weight of organically modified zirconium dioxide, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl(2,4,6-triformyl)phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane are put into a reaction kettle and stirred. The temperature is controlled between 25°C and 50°C, the stirring speed is 1500rpm, and the stirring time is 4h to obtain component B.

[0101] Product preparation: Component A and component B are added into a reaction kettle in a ratio of 1:1 and stirred. The temperature is controlled at 20°C and the stirring speed is 1500 rpm. Stir for 5 minutes to obtain a curing adhesive composition.

[0102] Comparative Example 1:

[0103] 18 parts by weight of bisphenol A diglycidyl ether diacrylate, 52 parts by weight of bisphenol A epoxy diacrylate, 10 parts by weight of o-phenylphenoxyethyl acrylate, 30 parts by weight of 4-biphenylmethanol acrylate, 75 parts by weight of organically modified zirconium dioxide, 1 part by weight of vinyltrimethoxysilane, 12 parts by weight of isophoronediamine, 4 parts by weight of diphenyl (2,4,6-triformyl) phosphine oxide and 2 parts by weight of hydroxyl-containing polyether-modified polydimethylsiloxane were put into a reaction kettle and stirred. The temperature was controlled between 25° C. and 50° C., the stirring speed was 1500 rpm, and the stirring time was 6 hours to obtain a curing adhesive composition.

[0104] Performance testing:

[0105] For the curing adhesive compositions prepared in Examples 1-14 and Comparative Example 1, the viscosity at 25°C was tested using a viscometer; the mixture of Examples 1-14 and Comparative Example 1 was coated on a substrate, UV cured for 6 seconds, and thermally cured for 1.5 hours to form a film with a thickness of 10 μm; the linear expansion coefficient was tested using a thermal expansion coefficient meter; and the hardness was tested using a universal testing machine. The test results are shown in Table 1 below:

[0106] Table 1

[0107]

[0108] As can be seen from the above table, the high refractive index optical adhesive obtained by the present invention using acrylic resin, acrylate, epoxy resin, metal oxide nanoparticles, photoinitiator and auxiliary agent containing specific reactive groups has a viscosity of 500cps-800cps at room temperature and can be used in coating, spraying, spin coating and other processes. As can be seen from Examples 1-14 and Comparative Example 1, the optical adhesive composition provided by the present invention has a lower thermal expansion coefficient and better mechanical properties for the obtained adhesive layer. Due to the presence of acrylic resin with reactive functional groups in component A, the degree of cross-linking with the resin in component B during UV curing is increased. After thermal curing is complete, the curing cross-linking density of the resin component in the overall component is relatively high, thereby improving the comprehensive properties of the refractive index, light transmittance, hardness, etc. after the photocurable composition is cured to form an optical film. It is a high refractive index optical adhesive with a stable system and excellent performance after curing into a film.

[0109] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An optical adhesive composition, characterized in that: The invention comprises two components, A and B, wherein the component A comprises 10wt% to 60wt% of acrylic resin A, 20wt% to 70wt% of a first inorganic filler, and 0wt% to 20wt% of a functional additive; the component B comprises 20wt% to 50wt% of an acrylate B, 30wt% to 70wt% of a second inorganic filler, 1wt% to 25wt% of a curing agent, and 0wt% to 3wt% of a functional additive; The acrylic resin A at least comprises an alkyl (meth)acrylate, an alkyl (meth)acrylate ether or an aryl (meth)acrylate containing one or more reactive groups, wherein the reactive groups are selected from any one or more of hydroxyl, epoxy or carboxyl groups; and the curing agent at least comprises a photocuring agent.

2. The optical adhesive composition according to claim 1, characterized in that: The component A also contains 20wt%-70wt% of epoxy resin; The curing agent also includes a thermal curing agent.

3. The optical adhesive composition according to claim 1, characterized in that: The acrylate B comprises an alkyl (meth)acrylate, an alkyl (meth)acrylate ether or an aryl (meth)acrylate; The acrylic resin A and the acrylate B are the same as or different from each other.

4. The optical adhesive composition according to any one of claims 1 to 3, characterized in that: The (meth)acrylic acid alkyl ester is a C1-C 20 Alkyl monofunctional (meth) acrylate or having C1-C 20 Alkylene multifunctional (meth)acrylates; The (meth) acrylic acid alkyl ether ester is a C1-C 20 Alkyl monofunctional (meth) acrylate, or C1-C 20 Alkylene multifunctional (meth)acrylates; The (meth)acrylate is a C6-C 30 A monofunctional (meth)acrylate of an aromatic group, or a C6-C 30 A polyfunctional (meth)acrylate of an aromatic group, wherein the aromatic group is directly connected to the (meth)acrylate by a single bond, or is connected via a C1-C6 alkyl group, or is connected via a C1-C6 alkyl ether group.

5. The optical adhesive composition according to claim 2, characterized in that: The epoxy resin is an epoxy resin with an alicyclic or aromatic backbone and two or more glycidyl ether groups, glycidyl esters or dehydrated glyceryl esters at the ends.

6. The optical adhesive composition according to claim 5, characterized in that: The epoxy resin is selected from any one or more combinations of bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, novolac epoxy resin, glycidyl ester epoxy resin or glycidyl ether epoxy resin.

7. The optical adhesive composition according to claim 2, characterized in that: The thermal curing agent includes any one or more combinations of polythiol, amine curing agent or acid anhydride curing agent.

8. The optical adhesive composition according to claim 1, characterized in that: The first inorganic filler is selected from one or more combinations of organically modified or unmodified metal oxides or silicon dioxide; The second inorganic filler is selected from one or more combinations of organically modified or unmodified metal oxides or silicon dioxide; The first inorganic filler and the second inorganic filler are the same or different.

9. The optical adhesive composition according to claim 1, characterized in that: The functional additives include any one or a combination of defoaming agent, dispersant, leveling agent, silane coupling agent or thixotropic agent; The silane coupling agent contains at least one functional group of vinyl, epoxy or amino.

10. A glue layer, characterized in that: The optical adhesive composition according to any one of claims 1 to 9 is pre-cured under ultraviolet light and then cured at a temperature of 100-130°C, wherein the weight ratio of component A to component B is (1-1.5):1.

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