阅读说明：本技术 一种夜视兼容薄膜及其制备方法和应用 (Night vision compatible film and preparation method and application thereof ) 是由 李虹 于 2020-11-03 设计创作，主要内容包括：本发明属于材料领域,公开了一种夜视兼容薄膜及其制备方法和应用。该夜视兼容薄膜,包括一层透明基材以及涂覆在透明基材上的涂层；涂层主要由丙烯酸树脂、氨基树脂、纳米TiO_2溶胶、氧化石墨烯、紫外吸收剂、填料、树脂固化剂和溶剂制得。该夜视兼容薄膜在400nm-630nm范围内的光线透过率高,防紫外线能力强,在400nm-630nm下的光透过率在55％以上；在660nm-930nm下的光透过率在1.0％以下；在320-400nm下的光透过率在1.2％以下。该夜视兼容薄膜具有良好的耐水雾和耐盐雾性能,能够适应恶劣环境,应用场景广泛。该夜视兼容薄膜能够应用于夜视仪。(The invention belongs to the field of materials,a night vision compatible film, a method for making the same and applications thereof are disclosed. The night vision compatible film comprises a layer of transparent base material and a coating coated on the transparent base material; the coating mainly comprises acrylic resin, amino resin and nano TiO 2 Sol, graphene oxide, an ultraviolet absorbent, a filler, a resin curing agent and a solvent. The night vision compatible film has high light transmittance in the range of 400nm-630nm and strong ultraviolet resistance, and the light transmittance under the range of 400nm-630nm is more than 55 percent; the light transmittance at 660nm-930nm is below 1.0%; the light transmittance at 320-400nm is below 1.2%. The night vision compatible film has good water mist resistance and salt mist resistance, can adapt to severe environment, and is wide in application scene. The night vision compatible film can be applied to a night vision device.)

1. A night vision compatible film is characterized by comprising a transparent substrate and a coating coated on the transparent substrate; the coating mainly comprises acrylic resin, amino resin and nano TiO₂Sol, graphene oxide, an ultraviolet absorbent, a filler, a resin curing agent and a solvent.

2. The night vision compatible film of claim 1, wherein the coating is made from the following raw materials in parts by weight:

3. the night vision compatible film as claimed in claim 1 or 2, wherein the acrylic resin has a molecular weight of 2000-.

4. The night vision compatible film of claim 1 or 2, wherein the amino resin is at least one of urea formaldehyde resin, melamine formaldehyde resin or polyamide polyamine epichlorohydrin.

5. Night vision compatible film according to claim 1 or 2, characterized in that the nano TiO is₂Preparation of solThe preparation method comprises the following steps:

(1) dissolving butyl titanate in alcohol, adding alcohol amine, and mixing to obtain a mixed solution A;

(2) dissolving a catalyst in an alcohol solution, adding the solution into the mixed solution A, heating and reacting to prepare the nano TiO₂And (3) sol.

6. The night vision compatible film according to claim 5, wherein the mass ratio of butyl titanate, alcohol and alcohol amine in step (1) is 1: (20-40): (1-2).

7. The method of producing a night vision compatible film as claimed in any one of claims 1 to 6, comprising the steps of:

(1) mixing the acrylic resin, amino resin and nano TiO₂Adding the sol, the graphene oxide, the ultraviolet absorbent and the filler into a solvent, stirring for the first time, adding the resin curing agent, and stirring for the second time to obtain a coating material;

(2) and coating the coating material on one or two surfaces of the transparent substrate, drying and curing to obtain the night vision compatible film.

8. The preparation method according to claim 7, wherein the first stirring speed in step (1) is 200-500 rpm, and the stirring time is 30-60 min; the second stirring speed is 50-180 r/min, and the stirring time is 20-40 min.

9. An apparatus comprising the night vision compatible film of any one of claims 1-6.

10. A night vision device comprising the night vision compatible film of any one of claims 1 to 6.

Technical Field

The invention belongs to the field of materials, and particularly relates to a night vision compatible film, and a preparation method and application thereof.

Background

Night vision is a photoelectric technology for night observation by means of photoelectric imaging devices. The near infrared region is a spectral response region of night vision products such as night vision goggles. At present, visible light such as an incandescent lamp or a common light emitting diode is generally used as a light source for illumination, high spectral energy radiation exists in a near infrared region, interference is caused to a Night Vision Imaging System (NVIS) in a night vision mode, imaging effect is seriously influenced, and even images cannot be recognized. The night vision compatible technology solves the problems, and eliminates light and radiation which are emitted by an illumination system in the equipment and interfere the work of the night vision device through a certain technical means, so that the normal work of the night vision device is ensured.

The night vision compatible material mainly has strong absorption or separation effect on light rays in a red light region and a near infrared region within 660nm-930nm, and can ensure that the light rays within 400nm-630nm have enough transmittance. However, the light transmittance of the existing night vision compatible material in the range of 400nm-630nm is still not high, the ultraviolet resistance is weak, the water mist resistance and the salt mist resistance are poor, the material cannot adapt to severe environment, and the application scene cannot meet higher requirements.

Therefore, in order to ensure the normal operation of night equipment and to make the application scene of the night equipment wider, it is necessary to provide an ultraviolet-proof night vision compatible film which has the capabilities of water mist resistance and salt mist resistance and strong adaptability to severe environments.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a night vision compatible film and a preparation method thereof, and also provides an application of the night vision compatible film. The night vision compatible film has high light transmittance in the range of 400-630nm, strong ultraviolet resistance, water mist resistance and salt mist resistance, can adapt to severe environment and has wide application scenes.

A night vision compatible film comprises a transparent substrate and a coating layer coated on the transparent substrate; the coating mainly comprises acrylic resin, amino resin and nano TiO₂Sol, graphene oxide, an ultraviolet absorbent, a filler, a resin curing agent and a solvent.

When the film is prepared, amino resin and acrylic resin are matched for use, and a three-dimensional network structure formed by crosslinking is adopted, so that the film has high toughness; by utilizing the hydrophilicity of the acrylic resin, when the film is formed, water molecules are spread on the surface to form a transparent water film so as to play an antifogging effect; by adding nano TiO₂The compactness of the sol and the graphene oxide is further increased in a three-dimensional network structure formed by the resin, so that the performance of the sol and the graphene oxide is improved, particularly the salt spray resistance; meanwhile, nano TiO with uniform particle size distribution is adopted₂The sol, the graphene oxide and the ultraviolet absorbent are used in a matched manner, so that the blocking effect on ultraviolet light can be enhanced under the condition of good light transmission capacity; the graphene oxide has good dispersibility, contains oxygen functional groups, can be connected with various molecules, can increase the compatibility of each component, and ensures that the prepared film has uniform texture, high transparency and high light transmittance in the range of 400-630 m.

Preferably, the coating is mainly prepared from the following raw materials in parts by weight:

further preferably, the coating is mainly prepared from the following raw materials in parts by weight:

preferably, the raw materials for preparing the coating also comprise a near infrared absorbent; further preferably, the near-infrared absorbent is one or more of thiodiene type nickel dye, methyl cyanine type dye and phthalocyanine type dye.

Preferably, the molecular weight of the acrylic resin is 2000-. The acrylic resin is obtained by polymerizing at least three of methyl methacrylate, methyl acrylate, butyl acrylate or ethyl acrylate.

Preferably, the amino resin is at least one of urea-formaldehyde resin, melamine-formaldehyde resin or polyamide polyamine epichlorohydrin.

The nano TiO₂The preparation method of the sol comprises the following steps:

(1) dissolving butyl titanate in alcohol, adding alcohol amine, and mixing to obtain a mixed solution A;

(2) dissolving a catalyst in an alcohol solution, adding the solution into the mixed solution A, heating and reacting to prepare the nano TiO₂And (3) sol.

Preferably, the mass ratio of the butyl titanate, the alcohol and the alcohol amine in the step (1) is 1: (20-40): (1-2); reasonably proportioning nano TiO prepared from various raw materials₂Sol of nano TiO₂The sol has more uniform particle size distribution, particle size range of 30-50nm, average particle size of 45.3nm, good ultraviolet blocking effect, and low ultraviolet transmittance.

Preferably, the temperature of the reaction in step (2) is 57-65 ℃.

Preferably, the nano TiO₂The preparation method of the sol comprises the following steps:

(1) dissolving butyl titanate in absolute ethyl alcohol, adding triethanolamine, and mixing to obtain a mixed solution A;

(2) dissolving the catalyst in an ethanol water solution, adding the solution into the mixed solution A, heating and reacting to obtain the nano TiO2 sol.

The ultraviolet absorbent is benzotriazole UV-360, benzotriazole UV-326 or benzophenone UV-531.

Preferably, the resin curing agent is at least one selected from the group consisting of tert-butyl peroxybenzoate, dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and azobisisobutyronitrile.

Preferably, the filler is at least one of nano calcium carbonate, nano zinc oxide or nano magnesium carbonate.

Preferably, the solvent is at least one selected from chloroform, dichloromethane, toluene and ethylene glycol.

Preferably, the transparent substrate is a polyester film, such as a polyacrylate film or a polycarbonate film.

A preparation method of a night vision compatible film comprises the following steps:

(1) mixing the acrylic resin, amino resin and nano TiO₂Adding the sol, the graphene oxide, the ultraviolet absorbent and the filler into a solvent, stirring for the first time, adding the resin curing agent, and stirring for the second time to obtain a coating material;

(2) and coating the coating material on one or two surfaces of the transparent substrate, drying and curing to obtain the night vision compatible film.

Preferably, the speed of the first stirring in the step (1) is 200-500 r/min, and the stirring time is 30-60 min; the second stirring speed is 50-180 r/min, and the stirring time is 20-40 min. The purpose of the first stirring is to mix the raw materials, and a higher stirring speed is needed so as to mix the raw materials more uniformly; and the second stirring is carried out after the resin curing agent, and the excessively high stirring speed is not favorable for forming a three-dimensional network structure and even can cause part of the structure to be broken. The research shows that the speed of the second stirring cannot be higher than that of the first stirring, and the stirring time is not easy to be overlong.

Preferably, the drying process in the step (2) is drying at 15-40 ℃; the curing temperature is 70-95 ℃, and the curing time is 3-6 hours.

Preferably, the drying and curing process is performed under vacuum.

A device comprising a night vision compatible film as described herein.

A night vision device comprising a night vision compatible film according to the present invention.

Compared with the prior art, the invention has the following beneficial effects:

(1) the night vision compatible film has high light transmittance in the range of 400nm-630nm and strong ultraviolet resistance, and the light transmittance under the range of 400nm-630nm is more than 55 percent, for example, can reach 60 percent; the light transmittance at 660nm-930nm is below 1.0 percent and is as low as 0.5 percent; the light transmittance at 320-400nm is less than 1.2%, for example, as low as 0.08%.

(2) The night vision compatible film has good water mist resistance and salt mist resistance, can adapt to severe environment, and is wide in application scene.

Detailed Description

In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.

The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.

Example 1

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, stirring at 150 rpm for the second timeAnd stirring for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 2

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of an ultraviolet-proof night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 40 parts of absolute ethyl alcohol, adding 2 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at 65 ℃ to prepare the nano TiO₂And (3) sol.

(2) Mixing butyl acrylate, urea-formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, a methyl cyanine dye, benzotriazole UV-360 and nano calcium carbonate into ethylene glycol, and stirring for the first time at a stirring speed of 400 revolutions per minute for 50 minutes; adding tert-butyl peroxybenzoate, and stirring for the second time at the stirring speed of 200 revolutions per minute for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polycarbonate film, drying at 35 ℃ in vacuum, curing for 4 hours at 90 ℃ in vacuum after a solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 3

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 20 parts of absolute ethyl alcohol, adding 1 part of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.3 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at 65 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl acrylate, polyamide polyamine epoxy chloropropane and nano TiO₂Adding the sol, graphene oxide, phthalocyanine dye, benzotriazole UV-360 and nano magnesium carbonate into chloroform, stirring for the first time at the stirring speed of 250 revolutions per minute for 60 minutes; adding azodiisobutyronitrile, and stirring for the second time at the stirring speed of 100 revolutions per minute for 40 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 35 ℃ in vacuum, curing for 5 hours at 80 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 4

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Mixing methyl methacrylate and tri-methyl methacrylateCyanuramide-formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 150 rpm for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 5

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 150 rpm for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 6

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 150 rpm for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 7

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 150 rpm for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 8

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 2 parts of butyl titanate in 30 parts of absolute ethyl alcohol, adding 2.5 parts of triethanolamine, and mixing to obtain a mixed solution A; 0.5 part of catalyst is dissolved in an aqueous ethanol solutionAdding into the mixed solution A, reacting for 1 hour at 60 ℃ to obtain the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 150 rpm for 30 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Example 9

A night vision compatible film comprises a layer of transparent substrate polyacrylate film and a coating coated on the transparent substrate, wherein the coating is mainly prepared from the following raw materials:

a preparation method of a night vision compatible film comprises the following steps:

(1) dissolving 1 part of butyl titanate in 30 parts of absolute ethyl alcohol, adding 1.5 parts of triethanolamine, and mixing to obtain a mixed solution A; dissolving 0.5 part of catalyst in ethanol water solution, adding the solution into the mixed solution A, and reacting for 1 hour at the temperature of 60 ℃ to prepare the nano TiO₂And (3) sol.

(2) Methyl methacrylate, melamine formaldehyde resin and nano TiO₂Adding the sol, graphene oxide, thiodiene type nickel dye, benzotriazole UV-326 and nano zinc oxide into dichloromethane, stirring for the first time at the stirring speed of 300 revolutions per minute for 50 minutes; adding dibenzoyl peroxide, and stirring for the second time at the stirring speed of 300 revolutions per minute for 50 minutes to obtain the coating material.

And coating the coating material on one surface of a cleaned polyacrylate film, drying at 25 ℃ in vacuum, curing for 5 hours at 75 ℃ in vacuum after the solvent is volatilized, and thus obtaining the ultraviolet-proof night vision compatible film.

Application example 1

A night vision device having a lens with a night vision compatible film produced in example 1 of the present invention.

Application example 2

A night vision compatible film produced in example 1 of the present invention was provided on a lens of a probe.

Comparative example 1

Comparative example 1 is different from example 1 in that the nano TiO is not added in the preparation of comparative example 1₂The sol, the remaining raw materials and the preparation method were the same as in example 1.

Comparative example 2

Comparative example 2 is different from example 1 in that graphene oxide is not added in the preparation of comparative example 2, and the rest of the raw materials and the preparation method are the same as those of example 1.

Comparative example 3

Comparative example 3 is different from example 1 in that in comparative example 3, methyl methacrylate in example 1 is replaced with an equivalent amount of bisphenol a type epoxy resin, and the remaining raw materials and preparation method are the same as those in example 1.

Product effectiveness testing

The films obtained in examples 1 to 9 and comparative examples 1 to 3 were subjected to the performance test as follows:

1. the light transmittance of the film in the wavelength ranges of 320-400nm, 400-630nm and 660-930 nm is tested.

2. And (3) testing the waterproof fog performance: the film was tested using a light transmittance haze tester (model: WGT-S, Shanghai Shenguang Co., Ltd.); the samples were pretreated in a refrigerator at about-20 ℃ for 1h and then rapidly placed on boiling water (distance: about 5cm) for testing.

3. Salt spray resistance test: and (3) placing the film in a NaCl solution with the mass fraction of 3% -5%, observing the corrosion condition, and recording the hours for corrosion resistance.

The test results are shown in Table 1.

TABLE 1 film Performance test results

As can be seen from Table 1, the night vision compatible film obtained in example is significantly superior in various properties to the film obtained in comparative example.