High refractive index resin and method for preparing the same, uv adhesive and method for preparing the same, thin film

Abstract

The application relates to the technical field of chemistry, and discloses a high-refractive resin, a preparation method of the high-refractive resin, a UV glue, a preparation method of the UV glue and a film. The high-refractive resin is prepared from components with a molar ratio of titanium alkoxide and acid containing a terminal double bond, and the molar ratio of the two is 1:1-1:4. The application can prepare a high-refractive resin, and the high-refractive resin is used to prepare a UV glue and a film. The production process of each procedure is simple, the curing speed is fast, the film with a thickness of 200 nm can be prepared, the refractive index is high, the film has excellent light transmittance, and the film can be widely applied to the field of optical devices.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of chemical technology, in particular to a high refractive index resin and a preparation method thereof, a UV glue and a preparation method thereof, and a film. BACKGROUND

[0002] High refractive index optical films are widely used in new optical nanodevices, such as planar waveguide circuits, nanolasers, solar cells and anti-reflection coatings, etc. In these applications, in addition to the basic parameter of refractive index, other properties such as Abbe number, light transmittance, uniformity, processability and thermal stability are also important.

[0003] There are two methods to obtain high refractive index materials at present: one is to introduce aromatic groups, halogens, amines or sulfur-containing functional groups into organic polymers, but the introduction of these groups is accompanied by a decrease in optical transparency and a deepening of color in the visible region, and the solubility and processability are poor, thereby limiting their practical application in optical and optoelectronic devices; the other method is to dope high refractive index nanoparticles such as TiO2, ZnS, CeO2, ZrO2, ZnO, etc. in an organic polymer matrix, but this method requires a high enough proportion of nanoparticles to meet the refractive index requirement, resulting in a serious non-uniformity of the prepared composite film, poor light transmittance and poor processability.

[0004] Therefore, the skilled person in the art is committed to developing a high refractive index resin and a preparation method thereof, a UV glue and a preparation method thereof, and a film, and the film prepared by the present application has high refractive index, good light transmittance and uniformity. SUMMARY

[0005] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present application is to provide a high refractive index resin and a preparation method thereof, a UV glue and a preparation method thereof, and a film, and the film prepared by the resin or the UV glue of the present application has high refractive index, good light transmittance and uniformity.

[0006] To achieve the above-mentioned purpose, the present application provides a high refractive index resin, which is prepared by using components including the following molar ratio:

[0007] The molar ratio of titanium alkoxide and acid containing terminal double bond is 1:1-1:4. The titanium alkoxide is reacted with the acid containing terminal double bond to obtain a multifunctional TiO2 resin, i.e. the high refractive index resin of the present application, which is used for preparing a UV glue, and the film prepared by the UV glue has good uniformity, high refractive index and high light transmittance.

[0008] Preferably, the titanium alkoxide is one or more of tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate; the acid containing terminal double bond is one or more of methacrylic acid, 3-butenoic acid, beta-(acryloyloxy)propionic acid. The molar ratio of titanium alkoxide to acid is 1:1 to 1:4, respectively, to obtain TiO2 resin with a functional group of 1 to 4.

[0009] The application also provides a preparation method of the high refractive index resin as described above, comprising the following steps: stirring the titanium alkoxide and the acid containing terminal double bond at room temperature for 1 to 5 hours, and then obtaining a transparent liquid after removing part or all of the solvent at 30 to 70°C, thereby obtaining the high refractive index resin.

[0010] The application also provides a UV glue, comprising the following components in mass ratio:

[0011] The high refractive index resin as described above is 30 to 70 parts, the acrylic monomer is 20 to 60 parts, the organic solvent is 0 to 40 parts, the photoinitiator is 1 to 4 parts, and the additive is 0.1 to 2 parts, wherein the additive is one or both of a leveling agent and a defoaming agent.

[0012] Preferably, the acrylic monomer is one or more of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, o-phenylphenoxyethyl acrylate, tripropyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, and 4-acryloylmorpholine.

[0013] Preferably, the organic solvent is one or more of toluene, isopropyl alcohol, propylene glycol methyl ether acetate, and methoxyethanol. In the application, the organic solvent mainly functions to adjust the viscosity of the glue for construction, and is added according to actual conditions.

[0014] Preferably, the photoinitiator is one or more of benzoin dimethyl ether, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0015] Preferably, the mass ratio of the components is as follows:

[0016] The high refractive index resin as described above is 30 to 40 parts, the acrylic monomer is 26 to 60 parts, the organic solvent is 0 to 40 parts, the photoinitiator is 1 to 3 parts, and the additive is 0.1 to 1 part.

[0017] The application also provides a preparation method of the UV glue as described above, comprising the following steps: stirring the high refractive index resin and the acrylic monomer at room temperature until they are uniformly mixed, adding the photoinitiator and the additive in a light-proof environment and stirring until they are uniformly mixed, and finally adding the organic solvent and stirring until it is uniformly diluted, thereby obtaining the UV glue.

[0018] The application also provides a film prepared by using the UV glue as described above.

[0019] The present application has the advantages that the present application can prepare a high refractive index resin, and use the resin to prepare a UV glue and a film, each process is simple, the curing speed is fast, the film with a thickness of 200 nm can be prepared, the film has high refractive index and excellent light transmittance, and can be widely applied in the field of optical devices. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a photo of the high refractive index film prepared in Example 4 of the present application. DETAILED DESCRIPTION

[0021] The present application will be further described below in combination with the drawings and examples. The examples described herein are only used to explain the present application, and do not limit the present application. The present application is not particularly described as the ordinary commercial products.

[0022] The present application provides a high refractive index resin, which is prepared by using components with the following molar ratio:

[0023] The molar ratio of the titanium alkoxide and the acid containing terminal double bond is 1:1-1:4. The titanium alkoxide is one or more of tetraethyl titanate, tetrabutyl titanate and tetraisopropyl titanate; the acid containing terminal double bond is one or more of methacrylic acid, 3-butenoic acid and β-(acryloyloxy)propionic acid. The molar ratio of the titanium alkoxide and the acid is 1:1-1:4, and the TiO2 resin with the functional group of 1-4 is obtained.

[0024] The present application also provides a preparation method of the high refractive index resin as described above, which comprises the following steps: stirring the titanium alkoxide and the acid containing terminal double bond at room temperature for 1-5 h, and removing part or all of the solvent at 30-70°C to obtain a transparent liquid, and the preparation is completed.

[0025] The present application also provides a UV glue, which comprises the following components with the following mass ratio:

[0026] High refractive resin 30-70 parts, acrylic monomer 20-60 parts, organic solvent 0-40 parts, photoinitiator 1-4 parts, additive 0.1-2 parts, wherein the additive is one or both of leveling agent and defoaming agent. The acrylic monomer is one or more of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, o-phenylphenoxyethyl acrylate, tripropyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, and 4-acryloylmorpholine. The organic solvent is one or more of toluene, isopropyl alcohol, propylene glycol methyl ether acetate, and methoxyethanol. The photoinitiator is one or more of benzpinacol, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0027] The application also provides a preparation method of the UV glue as described above. The high refractive resin and the acrylic monomer are stirred uniformly at room temperature, the photoinitiator and the additive are added and stirred uniformly in a light-proof environment, and finally the organic solvent is added and diluted uniformly, thereby obtaining the product.

[0028] The application also provides a thin film prepared by using the UV glue as described above. The preparation method is as follows.

[0029] The high refractive UV glue is added dropwise on a substrate, is spin-coated on a spin coater at 1000-5000 rpm for 30-180 seconds, is baked on a heating plate at 50-100 degrees for 1 minute, is cured after irradiation by a UV lamp for 1-2 minutes, and thereby a high refractive thin film is obtained.

[0030] In order to further illustrate the application, the following examples are provided.

[0031] Example 1

[0032] 1) Preparation of high refractive resin: 25.5 g of tetraisopropyl titanate (90 mmol) and 51.8 g of β-(acryloyloxy)propionic acid (360 mmol) are stirred at room temperature for 4 h, and all the solvent is removed at 50°C under reduced pressure to obtain a yellow liquid, which is the high refractive resin of the application, and the mass spectrometry data is m / z: 388.15.

[0033] 2) Preparation of UV glue: in a flask, 38.9 parts of the high refractive resin described above, 30 parts of acrylic monomer o-phenylphenoxyethyl acrylate, and 30 parts of tripropyleneglycol diacrylate are added by mass, stirred at room temperature for 12 h, and stirred uniformly. Then 1 part of photoinitiator 1-hydroxycyclohexyl phenyl ketone and 0.1 part of leveling agent BYK-333 are added, and stirred uniformly in a light-proof environment, thereby obtaining the UV glue with high refractive index.

[0034] Example 2

[0035] 1) Preparation of high refractive resin: 30.6 g of tetrabutyl titanate (90 mmol) and 51.8 g of 3-butenoic acid (360 mmol) were stirred at room temperature for 4 h, and all the solvents were removed at 60°C under reduced pressure to obtain a yellow liquid, which was the high refractive resin. Mass spectral data m / z: 620.22.

[0036] 2) Preparation of UV glue: In a flask, 70 parts by mass of the above high refractive resin, 12 parts of acrylic monomer o-phenylphenoxyethyl acrylate, 12 parts of tripropylene glycol diacrylate were added, stirred at room temperature for 24 h, 4 parts of photoinitiator (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide, 1 part of leveling agent BYK-333, 1 part of defoaming agent BYK-024 were added, and the mixture was stirred uniformly in a dark environment to obtain the UV glue with high refractive index.

[0037] Example 3

[0038] 1) Preparation of high refractive resin: 30.6 g of tetrabutyl titanate (90 mmol) and 25.9 g of β-(acryloyloxy)propionic acid (180 mmol) were stirred at room temperature for 2 h, and all the solvents were removed at 60°C under reduced pressure to obtain a yellow liquid, which was the high refractive resin. Mass spectral data m / z: 480.35.

[0039] 2) Preparation of UV glue: In a flask, 60 parts by mass of the above high refractive resin, 10 parts of acrylic monomer 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 10 parts of ethylene glycol dimethacrylate were added, stirred at room temperature for 24 h, 3 parts of photoinitiator (2,4,6-trimethylbenzoyl)diphenyl phosphine oxide, 1 part of leveling agent BYK-333, 16 parts of organic solvent toluene were added, and the mixture was stirred uniformly in a dark environment to obtain the UV glue with high refractive index.

[0040] Example 4

[0041] 1) Preparation of high refractive resin: 20.5 g of tetrabutyl titanate (90 mmol) and 25.9 g of 3-butenoic acid (180 mmol) were stirred at room temperature for 2 h, and all the solvents were removed at 50°C under reduced pressure to obtain a yellow liquid, which was the high refractive resin. Mass spectral data m / z: 364.53.

[0042] 2) Preparation of UV glue: in a flask, add high refractive resin 60 parts, acrylic monomer 9,9-bis[4-(2-acryloyloxyethoxy) phenyl] fluorene 15 parts, ethylene glycol dimethacrylate 15 parts, stir at room temperature for 24 h, add photoinitiator (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 2 parts, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1 part, leveling agent BYK-333 0.5 parts, defoaming agent BYK-024 0.5 parts, organic solvent propylene glycol methyl ether acetate 6 parts, stir uniformly in a light-proof environment to obtain UV glue with high refractive index.

[0043] Example 5

[0044] 1) Preparation of high refractive resin: 20.5 g of tetraethyl titanate (90 mmol) and 12.9 g of β-(acryloyloxy) propionic acid (90 mmol) were stirred at room temperature for 2 h, and all the solvents were removed under reduced pressure at 50°C to obtain a yellow liquid, which was the high refractive resin. The mass spectrometry data were m / z: 326.28.

[0045] 2) Preparation of UV glue: in a flask, add high refractive resin 30 parts, acrylic monomer 9,9-bis[4-(2-acryloyloxyethoxy) phenyl] fluorene 13 parts, ethylene glycol dimethacrylate 13 parts, stir at room temperature for 24 h, add photoinitiator (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide 2 parts, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1 part, leveling agent BYK-333 0.5 parts, defoaming agent BYK-024 0.5 parts, organic solvent propylene glycol methyl ether acetate 40 parts, stir uniformly to obtain UV glue with high refractive index.

[0046] Utility verification

[0047] Preparation of high refractive thin film:

[0048] The glue prepared in Examples 1 and 2 was dropped on a silicon wafer, and a film was formed by spin coating at 1000 rpm on a spin coater. The high refractive thin film was obtained after curing by UV lamp irradiation for 1 minute.

[0049] The glue prepared in Examples 3-5 was dropped on a silicon wafer, and a film was formed by spin coating at 3000 rpm on a spin coater. The high refractive thin film was obtained after curing by UV lamp irradiation for 1 minute on a heating plate at 80 degrees. The thin film prepared in Example 4 is shown in Figure 1

[0050] The high refractive thin films prepared from the UV glue of Examples 1-5 were measured for film thickness and refractive index by an ellipsometer.

[0051] The high refractive thin films prepared from the UV glue of Examples 1-5 were measured for transmittance by a transmittance tester. ​

[0052] The determination results are shown in the following table:

[0053] Film thickness 633 nm refractive index Transmittance Example 1 0.22 μm 1.620 97.5％ Example 2 0.92 μm 1.642 95％ Example 3 1.37 μm 1.666 94.6％ Example 4 0.61 μm 1.689 96.3％ Example 5 1.59 μm 1.704 94.2％

[0054] From the determination results of the above examples, it can be seen that the high-refractive UV glue prepared by the application can be used to prepare thin films with a thickness as low as 200 nm level, and the refractive index at 633 nm wavelength can be more than 1.70, while having excellent light transmittance, and can be widely applied in the field of optical devices.

[0055] The preferred embodiments of the application are described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and changes without creative work based on the concept of the application. Therefore, any technical solutions obtained by logical analysis, reasoning or limited experiments based on the existing technology according to the concept of the application should be within the protection scope determined by the claims.

Claims

1. A UV glue, characterized in that, The components include the following mass ratio: High refractive resin 30-70 parts, acrylic monomer 20-60 parts, organic solvent 0-40 parts, photoinitiator 1-4 parts, and auxiliary agent 0.1-2 parts, wherein the auxiliary agent is one or both of leveling agent and defoaming agent; The high refractive resin is prepared by using components with the following molar ratio: Titanium alkoxide and acid containing terminal double bond, the molar ratio of the two is 1:1-1:4; The titanium alkoxide is one or more of tetraethyl titanate, tetrabutyl titanate, and tetraisopropyl titanate; the acid containing terminal double bond is one or more of methacrylic acid, 3-butenoic acid, and β-(acryloyloxy) propionic acid; The preparation method of the high refractive resin comprises the following steps: stirring titanium alkoxide and acid containing terminal double bond at room temperature for 1-5 h, and then removing part or all of the solvent at 30-70°C to obtain a transparent liquid.

2. The UV adhesive of claim 1, wherein: The acrylic monomer is one or more of 9,9-bis[4-(2-acryloyloxyethoxy) phenyl] fluorene, o-phenylphenoxyethyl acrylate, tripropyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, and 4-acryloyl morpholine.

3. The UV adhesive of claim 1, wherein: The organic solvent is one or more of toluene, isopropyl alcohol, propylene glycol methyl ether acetate, and methoxyethanol.

4. The UV adhesive of claim 1, wherein: The photoinitiator is one or more of benzoin dimethyl ether, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

5. The UV adhesive of claim 1, wherein the UV adhesive is a UV curable adhesive. The mass ratio of the components is: The high refractive resin 30-40 parts, the acrylic monomer 26-60 parts, the organic solvent 0-40 parts, the photoinitiator 1-3 parts, and the auxiliary agent 0.1-1 parts.

6. A method of preparing the UV glue according to any one of claims 1 to 5, characterized by: The high refractive resin and the acrylic monomer are stirred uniformly at room temperature, the photoinitiator and the auxiliary agent are added and stirred uniformly in a dark environment, and finally the organic solvent is added and diluted uniformly.

7. A film characterized by, The UV glue is prepared by using any one of the UV glues in claims 1-5.

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