An acrylate monomer, UV curing glue and its preparation method and application

Abstract

The application provides an acrylic ester monomer, a UV curing adhesive, and a preparation method and application thereof. The preparation raw material of the acrylic ester monomer comprises a combination of a metal compound and an acrylic ester compound with a structure shown in formula I. The UV adhesive prepared by using the acrylic ester monomer has the advantages of low curing energy, and the optical film layer formed after curing has the advantages of high refractive index, and can be used as OLED light extraction material and various high-refractive-index optical film layer materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of adhesives, and particularly relates to an acrylate monomer, a UV curing glue, and a preparation method and application thereof. BACKGROUND

[0002] OLED, also known as organic electroluminescent display or organic light-emitting semiconductor, has the characteristics of lighter and thinner, high brightness, low power consumption, fast response, high definition, good flexibility and high luminous efficiency compared with LCD. The OLED device is composed of a substrate, a cathode, an anode, a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, an electron blocking layer, a hole blocking layer, a light-emitting layer and the like. OLED is a current type organic light-emitting device. Under the action of an electric field, the holes generated by the anode and the electrons generated by the cathode will move and be injected into the hole transport layer and the electron transport layer, respectively, and migrate to the light-emitting layer. When the two meet in the light-emitting layer, energy excitons are generated, thereby exciting light-emitting molecules to finally produce visible light. When the visible light escapes from the OLED device, due to the high refractive index of the device and the low refractive index of the outer film layer material, most of the emitted light will be lost in the form of total reflection, so a material for improving the light extraction efficiency is needed.

[0003] WO2020106884A discloses a high-refractive printing material for printing. The principle is to use a series of metal organic compounds such as alkyl titanate to graft some organic chain segments on the surface layer of metal atoms by high-pressure hydrothermal method, thereby preparing a batch of organic particles containing metal atoms. These organic particles are mixed with various monomers or resins to meet the printing requirements of Ink, and a high-refractive optical film layer is obtained after printing and UV curing, thereby improving the light extraction efficiency.

[0004] CN112105967A discloses a curable composition comprising an acrylate of Formula I: at least one multifunctional (meth)acrylate having a fused aromatic group, a heteroarylene group, a heteroalkylene group, an alkylene group, or an aralkylene group; and a photoinitiator. The composition has a refractive index of 1.63 or more at 532 nm when cured, is optically transparent, and has thermal stability such that the composition has a weight loss of 3.5% or less when heated at 250°C for 1 h.

[0005] However, the high-refractive printing material or the curable composition provided in the prior art is complex to operate and has high curing energy.

[0006] Therefore, it is an urgent technical problem in the field to develop an acrylate monomer with high refractive index, low curing energy and uniform distribution. SUMMARY

[0007] In view of the shortcomings of the prior art, the present invention aims to provide an acrylate monomer, a UV-curable adhesive, a preparation method thereof, and an application thereof. The raw materials for preparing the acrylate monomer include metal compounds and acrylate compounds. By hybridizing the metal element into the organic part, the refractive index of the prepared acrylate monomer is effectively increased, and the curing energy is reduced.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides an acrylate monomer, wherein the raw materials for preparing the acrylate monomer include a metal compound and an acrylate compound;

[0010] The acrylate compound has the structure shown in Formula I:

[0011]

[0012] Among them, X n Selected from H, C1-C10 alkyl (e.g., C2, C3, C4, C5, C6, C7, C8 or C9 alkyl) or C6-C12 aryl (e.g., C6, C7, C8, C9, C10 or C11 aryl),

[0013] R n Selected from any one of C6-C12 aryl groups (e.g., aryl groups of C6, C7, C8, C9, C10 or C11).

[0014] The raw materials for preparing acrylate monomers provided by this invention include a combination of metal compounds and acrylate compounds. By introducing the metal compound into the raw materials, the metal compound can react with the acrylate compounds, thereby successfully hybridizing the metal element into the organic part, and finally obtaining an acrylate monomer containing the metal element. The acrylate monomer containing the metal element has a high refractive index, and the UV-curable adhesive using the acrylate monomer has a low curing energy.

[0015] Preferably, the metal compound includes a metal chloride.

[0016] Preferably, the metal chloride includes any one of titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, vanadium chloride, aluminum chloride, or zinc chloride.

[0017] The acrylate monomer has the structure shown in Formula II:

[0018]

[0019] M is selected from any one of Ti, Zr, Hf, V, Al, or Zn;

[0020] X n is selected from any one of H, C1-C10 alkyl (e.g. C2, C3, C4, C5, C6, C7, C8, or C9 alkyl) or C6-C12 aryl (e.g. C6, C7, C8, C9, C10, or C11 aryl),

[0021] R n is selected from any one of C6-C12 aryl (e.g. C6, C7, C8, C9, C10, or C11 aryl).

[0022] As a preferred technical solution of the present application, the acrylate compound provided by the present application has the structure shown in Formula I, wherein the metal element M is selected from any one of Ti, Zr, Hf, V, Al or Zn. The above-mentioned specific metal elements have a larger atomic radius, which can make the obtained acrylate monomer have a higher refractive index, and can further reduce the UV curing energy of the UV curing adhesive containing the acrylate monomer of the present application.

[0023] Preferably, the acrylate monomer has the structures shown in E1-E4:

[0024]

[0025] In a second aspect, the present application provides a preparation method of the acrylate monomer as described in the first aspect, the preparation method comprising: reacting a metal compound and an acrylate compound to obtain the acrylate monomer.

[0026] In a third aspect, the present application further provides an intermediate for synthesizing the acrylate monomer as described in the first aspect, the intermediate having the structure shown in E3-1 or E4-1:

[0027]

[0028] In a fourth aspect, the present application provides a UV curing adhesive, the UV curing adhesive comprising a combination of the acrylate monomer as described in the first aspect, other unsaturated monomers and a photoinitiator.

[0029] Preferably, the mass ratio of the acrylate monomer and the other unsaturated monomers is 1:(0.5-1.5), for example 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3 or 1:1.4, etc.

[0030] Preferably, the other unsaturated monomer includes any one of phenyl acrylate, phenyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol acrylate, ethylene glycol methacrylate, 2-phenoxybenzyl acrylate, diphenyl methacrylate, 2-phenethyl acrylate, 2-phenylthioethyl acrylate, polydipentaerythritol hexaacrylate or azidodiphenyl phosphate or a combination of at least two thereof.

[0031] Preferably, the photoinitiator includes any one of diphenyl (2,4,6-trimethoxybenzoyl)-phosphine oxide (TPO), 1-hydroxycyclohexyl phenyl ketone (photoinitiator 184) or 2,2-azobis(2-methylpropionitrile) (AIBN) or a combination of at least two thereof.

[0032] Preferably, the UV curing adhesive further includes a leveling agent and / or a defoaming agent, for example, the leveling agent BYK361N, BYK3500 or BYK3501 can be selected.

[0033] In a fifth aspect, the present application provides a preparation method of the UV curing adhesive according to the fourth aspect, the preparation method comprising: mixing the acrylate monomer, the other unsaturated monomer, the photoinitiator, optionally the defoaming agent and optionally the leveling agent according to the first aspect to obtain the UV curing adhesive.

[0034] In a sixth aspect, the present application provides an application of the UV curing adhesive according to the fourth aspect as an OLED light extraction material or an optical film layer material.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] The preparation raw material of the acrylate monomer provided by the present application includes a metal compound and an acrylate compound. The metal compound reacts with the acrylate compound to obtain an acrylate monomer containing a metal element, and the acrylate monomer containing the metal element has a relatively high refractive index. The UV curing adhesive prepared by matching the acrylate monomer with other unsaturated monomers has the advantages of high refractive index and low curing energy, and can be applied as an OLED light extraction material or an optical film layer material. DETAILED DESCRIPTION

[0037] The technical solutions of the present application are further illustrated by the specific embodiments below. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0038] Example 1

[0039] An acrylate monomer E1, the reaction formula is as follows: An acrylate monomer E1, the reaction formula is as follows:

[0040]

[0041] The specific preparation method comprises the following steps: adding 500 mL of tetrahydrofuran into a three-neck flask, adding 23.3 g of zirconium tetrachloride, 50 g of triethylamine and 0.1 g of p-cresol under nitrogen protection, stirring for 30 min, adding 80 g of a tetrahydrofuran solution of an intermediate shown in E1-1 by using a constant-pressure dropping funnel, having a temperature rise phenomenon (temperature control is 20-25 °C), continuing to stir for 19 h after the dropping is completed, washing with water and dichloromethane, separating the liquid, washing the organic layer until neutral, drying with sodium sulfate, and evaporating the solvent under reduced pressure to obtain the acrylic ester monomer E1.

[0042] The mass spectrum data m / z of the acrylic ester monomer E1 is 854.19.

[0043] The theoretical value of the elemental analysis is as follows: C: 61.73%, H: 5.18%, O: 22.43%, and Zr: 10.66;

[0044] The measured value of the elemental analysis is as follows: C: 61.79%, H: 5.16%.

[0045] Example 2

[0046] An acrylic ester monomer E2, the reaction formula of which is as follows:

[0047]

[0048] The preparation method thereof is referred to the preparation method of E1, except that the compound shown in E1-1 is replaced by the compound shown in E2-1.

[0049] The mass spectrum data m / z of the acrylic ester monomer E2 is 910.25.

[0050] Example 3

[0051] An acrylic ester monomer E3, the preparation method thereof comprises the following steps (1) and (2):

[0052] (1) Synthesis of an intermediate E3-1, the reaction formula of which is as follows:

[0053]

[0054] The specific synthesis steps include: adding 500 mL of toluene, 14.8 g of 2-phenyl acrylic acid, 12 g of 2-phenyl oxirane, 1.5 g of tetrabutylphosphonium bromide (cas:3115-68-2), 0.2 g of 2,5-di-tert-butyl hydroquinone into a 1000 mL three-necked flask, slowly heating to reflux for 6 h, cooling, adding water to separate, washing the organic layer with water until neutral, concentrating to dryness under reduced pressure, and then separating by silica gel column chromatography, eluting with petroleum ether: ethyl acetate = 1:1 (volume ratio) to obtain 22.9 g of intermediate E3-1;

[0055] The mass spectrum data m / z of E3-1 is 268.11.

[0056] The nuclear magnetic resonance data 1H-NMR of E3-1 (Switzerland Bruker Company, Avance Ⅱ 400 MHz nuclear magnetic resonance spectrometer, CDCl3) is δ 7.47-7.16 (m, 10H), δ 6.35-6.21 (m, 2H), δ 5.18 (m, 1H), δ 4.78-4.50 (m, 2H), δ 1.63 (s, 1H);

[0057] (2) Synthesis of acrylic ester monomer E3, the reaction formula is as follows:

[0058]

[0059] The synthesis method refers to the synthesis of E1, except that the compound shown in E1-1 is replaced by the compound shown in E3-1.

[0060] The mass spectrum data m / z of the acrylic ester monomer E3 is 1158.31.

[0061] Example 4

[0062] An acrylic ester monomer E4, the preparation method thereof comprises steps (1) and (2):

[0063] (1) Synthesis of intermediate E4-1, the reaction formula is as follows:

[0064]

[0065] The synthesis method refers to the synthesis of E3-1, except that 2-phenyl oxirane is replaced by 2-biphenyl oxirane;

[0066] The mass spectrum data m / z of E4-1 is 268.11.

[0067] (2) Synthesis of acrylic ester monomer E4, the reaction formula is as follows:

[0068]

[0069] The synthesis method refers to the synthesis of E1, except that the compound shown as E1-1 is replaced by the compound shown as E4-1.

[0070] The mass spectrum data m / z of the acrylate monomer E4 is 1158.31.

[0071] Application Example 1

[0072] A UV curing adhesive, which comprises the following components by weight:

[0073]

[0074] The preparation method of the UV curing adhesive provided in the application example comprises: mixing an acrylate monomer E1, phenyl methacrylate, trimethylolpropane triacrylate, BYK361N and a photoinitiator 819 to obtain the UV curing adhesive.

[0075] Application Example 2

[0076] A UV curing adhesive, which is different from application example 1 only in that the acrylate monomer E1 obtained in example 1 is replaced by an acrylate monomer E2, and other components, amounts and preparation methods are the same as those of application example 1.

[0077] Application Example 3

[0078] A UV curing adhesive, which is different from application example 1 only in that the acrylate monomer E1 obtained in example 1 is replaced by an acrylate monomer E3, and other components, amounts and preparation methods are the same as those of application example 1.

[0079] Application Example 4

[0080] A UV curing adhesive, which is different from application example 1 only in that the acrylate monomer E1 obtained in example 1 is replaced by an acrylate monomer E4, and other components, amounts and preparation methods are the same as those of application example 1.

[0081] Comparative Application Example 1

[0082] A UV curing adhesive, which is different from application example 1 only in that the acrylate monomer E1 obtained in example 1 is not added, the addition amount of phenyl methacrylate is 50 parts by weight, the addition amount of trimethylolpropane triacrylate is 50 parts by weight, and other components, amounts and preparation methods are the same as those of application example 1.

[0083] Performance test:

[0084] (1) Viscosity: the UV curing adhesive is tested by using a BROOKFIELD viscometer;

[0085] (2) Refractive index: UV curing glue was coated on a glass substrate, and UV curing was performed using a 395 nm LED lamp at a curing energy of 1000 mJ / cm 2 , to obtain an optical film layer, and an ellipsometer (Wuhan Yiguang) was used to test the refractive index thereof.

[0086] The UV curing glue provided by application examples 1-4 and comparative application example 1 was tested according to the above test method, and the test results are shown in Table 1.

[0087] Table 1

[0088]

[0089] As can be seen from Table 1, the UV curing glue prepared by using the acrylate monomer provided by the present application has low curing energy, and the optical film layer after curing has a relatively high refractive index; and the UV curing glue provided in the prior art cannot be completely cured at a curing energy of 1000 mJ / cm 2 and 1500 mJ / cm 2 .

[0090] The applicant declares that the present application is illustrated by the above examples as an acrylate monomer, UV curing glue, and a preparation method and application thereof, but the present application is not limited to the above examples, i.e., it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement on the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc., all fall within the protection scope and disclosure scope of the present application.

Claims

1. An acrylate monomer, characterized by, The acrylate monomer has a structure shown in Formula II: Formula II; wherein X n is selected from any one of H, C1-C10 alkyl or C6-C12 aryl, R n any one selected from C6-C12 aryl; M is selected from any one of Ti, Zr, Hf.

2. An acrylate monomer characterized in that, The acrylate monomer has a structure shown in Formula II: 。 3. A UV-cured glue, characterized in that, The UV curing adhesive comprises the acrylate monomer, other unsaturated monomers and a photoinitiator as claimed in any one of claims 1-2.

4. The UV-curable glue according to claim 3, wherein, The mass ratio of the acrylate monomer and the other unsaturated monomers is 1:(0.5-1.5).

5. The UV-curable glue according to claim 3, wherein, The other unsaturated monomers comprise any one or a combination of at least two of phenyl acrylate, phenyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol acrylate, ethylene glycol methacrylate, 2-phenoxybenzyl acrylate, diphenyl methacrylate, 2-phenethyl acrylate and 2-phenylthioethyl acrylate.

6. The UV-curable glue of claim 3, wherein, The photoinitiator comprises any one or a combination of at least two of diphenyl (2,4,6-trimethoxybenzoyl)-phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and 2,2-azobis(2-methylpropionitrile).

7. The UV-curable glue according to claim 3, wherein, The UV curing adhesive further comprises a leveling agent and / or a defoaming agent.

8. Use of the UV curing adhesive as claimed in any one of claims 3-7 as an OLED light extraction material or an optical film layer material.

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