CN111361183A - A kind of anti-ultraviolet heat insulation inorganic nano solar film and preparation method thereof - Google Patents

Abstract

The invention discloses an anti-ultraviolet heat-insulating inorganic nano solar film and a preparation method thereof, and belongs to the field of thin film technology. The invention adds a heat-insulating coating containing cesium tungsten bronze nanoparticles to the heat-insulating adhesive layer, and adds a benzotriazine ultraviolet absorber to the anti-ultraviolet layer. The prepared solar film has excellent anti-scratch performance, an ultraviolet blocking rate greater than 99%, an infrared blocking rate of 50% to 99%, and a visible light transmittance of 30% to 80%. After a 600-hour aging test, the ultraviolet blocking rate and the infrared blocking rate do not decrease, the solar film does not bubble or turn yellow, and the peeling strength meets the national standard requirements. The preparation method of the solar film of the invention is simple and easy to operate. When in use, the outer release film can be torn off according to the size of the glass and pasted on the glass surface. The solar film can achieve the effect of anti-ultraviolet heat insulation and energy saving, and has a long service life.

Description

A kind of anti-ultraviolet heat insulation inorganic nano solar film and preparation method thereof

technical field

The invention relates to the technical field of thin films, in particular to an anti-ultraviolet heat insulation inorganic nano solar film and a preparation method thereof.

Background technique

Ultraviolet rays in sunlight have a wavelength range of 280nm to 400nm, with strong penetrability, which is easy to deposit melanin on human skin and cause skin cancer. Excessive ultraviolet radiation also has certain damage to human eyes, and can also lead to aging and fading of interior decorations. Reduces the service life of decorations. The wavelength of infrared light is between 760nm and 1mm, which has obvious thermal effect, which is easy to cause the temperature to rise, thus causing the temperature of the room or car to rise. However, unfilmed glass is used in general buildings and car windows. Although these glasses have good light transmission, they cannot block most of the ultraviolet and infrared rays of sunlight. Therefore, in order to avoid the adverse effects of ultraviolet and infrared light and improve the comfort of the indoor or car environment, people need to stick solar films on architectural glass or automotive glass. Solar film, also known as thermal insulation film, is generally made of aluminum, gold, copper, silver and other metals into a multi-layered and dense high thermal insulation metal film layer by vacuum spraying or magnetron sputtering technology, which can effectively Block sunlight radiation, reduce UV damage to the human body, reduce indoor temperature, and slow down the aging of indoor facilities.

In order to further improve the UV blocking effect of the solar film, a UV absorber can be added to the solar film material. At present, the commonly used UV absorbers are mainly benzophenones and benzotriazoles. Although these two types of UV absorbers have a certain UV absorption effect, there are still various deficiencies in application: benzophenones The UV blocking effect of UV absorbers is poor, and the maximum absorption wavelength is only concentrated in the UVB (275nm ~ 320nm) band, which cannot cover all UV bands; the UV blocking effect of benzotriazole UV absorbers is higher than that of benzophenones. The effect of the UV absorber is better, and its maximum absorption wavelength is in the UVA (320nm ~ 400nm) and UVB bands, but it has poor compatibility with the pressure-sensitive adhesive in the solar film. With the prolongation of the use time, it is easy to precipitate in the solar film to form snowflake-like spots, which leads to an increase in the haze of the film, which affects the vision, and also reduces the UV blocking rate and shortens the service life of the solar film. Ultraviolet absorber is a functional additive, and the functional additive should usually be arranged in the inner layer of the solar film to reduce the impact on the air and human body caused by the volatilization and oxidation of the additive. CN201310319014.5 discloses a window film adhered to the outside of the window glass, in which the ultraviolet absorber 2,4,6-tris(butoxyphenyl)-1,3,5-triazine is added to the window film Anti-scratch and wear-resistant layer, the ultraviolet absorber is exposed to the position where people are easy to touch, which has certain harmfulness, and also affects the service life of the scratch-resistant layer; Oxyphenyl)-1,3,5-triazine was not added to the inner layer, probably due to the poor compatibility of the triazine UV absorber with the inner pressure sensitive adhesive, and its life test was only 100h, After 100h, the UV blocking effect may decrease, and the aging resistance is poor.

In the design of the existing solar film, the traditional heat insulation method is mainly realized by adding dyes to the film, but this dyed film has poor heat insulation effect and is easy to fade. In the modern process, metal nanoparticles are uniformly spread on the surface of the PET film by using magnetron sputtering technology and vacuum thermal evaporation technology to form a coating. When the coating is thick, it not only affects the communication signal, but also has poor clarity and is easy to reflect light. Affects vision; and when the coating is thin, the thermal insulation effect is poor. CN201410857764.2 discloses a solar film and a preparation method thereof. Nano ATO or cesium tungsten bronze is used for heat insulation. Nano particles are dispersed in resin to form nano slurry, which is coated on the base film to form functional heat insulation. The coating thickness is thicker, generally more than 15 microns thick. Since the nanoparticles are larger than 100 nanometers, and it is difficult to disperse uniformly in the glue, it is easy to cause the haze to increase and affect the vision. CN201210285669.0 discloses an anti-ultraviolet high heat-insulating window film, which adopts the composition of nano-ATO and ITO for heat-insulation. The UV absorbers diffuse into each other in the two layers of glue, which affects the service life. ATO and cesium tungsten bronze heat-insulating nanoparticles used in some solar films are mixed in the scratch-resistant layer. Since the thickness of the scratch-resistant layer is below 5 microns, some nanoparticles with a size of tens of nanometers cannot be completely buried. The scratch-resistant layer floats on the surface, which will easily shorten the life of the scratch-resistant layer, and the exposure of heavy metals to the outer layer that people can easily touch will bring unknown risks.

SUMMARY OF THE INVENTION

The object of the present invention is to overcome the deficiencies of the prior art and provide a kind of anti-ultraviolet heat-insulating inorganic nano solar film, the solar film has high visible light transmittance, ultraviolet blocking rate and infrared blocking rate, scratch resistance Superior performance, stable properties of each component during use, and long service life.

To achieve the above object, the technical scheme adopted by the present invention is as follows:

An anti-ultraviolet heat-insulating inorganic nano-solar film, comprising a release film, an anti-ultraviolet layer, a first PET base film, a heat-insulating adhesive layer, a second PET base film and an anti-scratch and wear-resistant layer, which are closely adhered to one another in sequence. ;

The heat insulating adhesive layer contains nano heat insulating paint, and the nano heat insulating paint includes cesium tungsten bronze nanoparticles with an average particle size of less than 40 nm;

The anti-ultraviolet layer contains a benzotriazine type ultraviolet absorber, and the mass percentage of the benzotriazine type ultraviolet absorber in the anti-ultraviolet layer does not exceed 1%.

The benzotriazine type ultraviolet absorber used in the anti-ultraviolet layer of the present invention has good aging resistance and high ultraviolet absorption efficiency, and can absorb all ultraviolet wavelengths. Compared with benzotriazole-based UV absorbers, benzotriazine-based UV absorbers have better compatibility with all pressure-sensitive adhesives commonly used at present, and have stable properties during use, which effectively solves the problem of UV-resistant layers. The poor compatibility between the UV absorber and the adhesive makes it easy to precipitate in the solar film to form snowflake-like spots, which leads to the reduction of the UV blocking rate and the shortened service life of the solar film.

The invention adopts cesium tungsten bronze nanoparticles with an average particle size of less than 40nm as the main heat insulating material, which has small particle size and good dispersibility. The cesium tungsten bronze nanoparticles are uniformly dispersed in the resin by using nano-grinding technology and high-efficiency dispersant to form a coating. , and then mix the coating with other components of the thermal insulation adhesive layer, which solves the problem that cesium tungsten bronze nanoparticles are difficult to disperse in the adhesive layer. The thermal insulation adhesive layer with good thermal insulation performance is prepared by coating the cesium tungsten bronze nanoparticle coating on the base film. At the same time, the color of the solar film can be changed by changing the addition amount of cesium tungsten bronze nanoparticles, which can be used for the front window and side window of the car without adding other dyes. Adding cesium tungsten bronze nanoparticles to the thermal insulation adhesive layer can also prevent the cesium tungsten bronze nanoparticles from floating on the surface of the solar film and lead to heavy metal exposure and contact with people.

Cesium tungsten bronze nanoparticles have the physical properties of transparency and heat insulation of tin oxide nanoparticles (ATO), and at the same time, the ability to block infrared light in the near-infrared region with a wavelength below 1000nm is far greater than that of ATO and indium tin oxide nanoparticles (ITO). ) The blocking ability to infrared light, and it has efficient infrared blocking ability to near-infrared rays below 1000nm. The area most sensitive to the thermal sensation of human skin is the near-infrared region below 1000 nm. Therefore, cesium tungsten bronze nanoparticles are used as the main insulating material to prepare solar film, which can greatly improve the comfort of the human body, save energy, and realize indoor The effect of warm in winter and cool in summer provides a technical guarantee for creating a more comfortable, environmentally friendly and energy-saving indoor environment.

The solar film of the invention adopts the combination of benzotriazine ultraviolet absorber and cesium tungsten bronze nanoparticles. After the aging test, the ultraviolet and infrared blocking rate of the solar film does not decrease, the solar film does not blister and yellow, and has good Aging resistance.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano solar film of the present invention, the anti-ultraviolet layer further contains a benzotriazole type ultraviolet absorber, and a benzotriazine type ultraviolet absorber and a benzotriazole type ultraviolet absorber The sum of the mass percentages of the ultraviolet absorber in the anti-ultraviolet layer does not exceed 1%.

The anti-ultraviolet layer of the present invention can be used in combination with a benzotriazine type ultraviolet absorber and a benzotriazole type ultraviolet absorber, so as to reduce the use cost, but the combined dose does not exceed 1 wt%.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the anti-ultraviolet layer includes the following components in mass percentage: a mixture of benzotriazole-based ultraviolet absorbers and benzotriazine-based ultraviolet absorbers 0.1%～1%, adhesive 40%～55%, curing agent 0.05%～1%, toluene 25%～40% and ethyl acetate 15%～20%.

As a preferred embodiment of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the benzotriazole UV absorber is 2'-(2'-hydroxy-3'-tert-butyl-5'-methyl) phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy 5'-methylphenyl) benzotriazole, 2-(2'-hydroxy-3',5'-diterbutin phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole, 2-(2 At least one of '-hydroxy-3', 5'-di-tert-butylphenyl)-benzotriazole.

As a preferred embodiment of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the benzotriazine-based UV absorber is a hydroxyphenyltriazine-based compound, preferably, the benzotriazine-based UV absorber The agent is at least one of UV-400, UV-479A and UV-479B.

The inventors have tested and preferred hydroxyphenyltriazine compounds as benzotriazine ultraviolet absorbers, wherein the component of UV-400 is 2-[4-[2-hydroxy-3-tridecyloxypropyl] Oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-deca Dialkoxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine mixture; UV-479A and UV -479B is a series of products of BASF Tinuvin479, which is a synthetic hydroxyphenyltriazine (HPT) UV absorber.

The mechanism of action of UV-400, UV-479A, and UV-479B is: before absorbing ultraviolet light, the absorber exists in the form of phenolic compounds, the electron density of oxygen atoms is much greater than that of nitrogen atoms, and the absorption of ultraviolet light makes electrons Density shifts primarily from oxygen atoms to nitrogen atoms, a form that is unstable and can convert excess energy into heat to return to a more stable state, a highly efficient interconversion process that can be repeated almost indefinitely. The more oxygen atoms contained in the UV absorber molecule, the better the UV absorption effect and the stronger the light resistance. UV400 and UV479 series UV absorbers contain more oxygen atoms than 2,4,6-tris(butoxyphenyl)-1,3,5-triazine, so they have higher UV blocking effect and excellent Aging resistance. UV400 and UV479 series compounds can provide excellent properties in coatings, such as extremely high extinction coefficient, high light life performance, high thermal stability of coatings, and low volatility under extreme environmental conditions. Suitable for use in combination with other benzotriazole UV absorbers.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the heat-insulating adhesive layer further contains a benzotriazine ultraviolet absorber. The heat insulating adhesive layer of the present invention adopts the combination of benzotriazine ultraviolet absorber and cesium tungsten bronze nanoparticles, which can effectively improve the ultraviolet blocking effect and heat insulation performance of the solar film, has excellent aging resistance, and has no The problem of thermal nanoparticles and UV absorbers affecting the service life due to mutual diffusion.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the heat-insulating adhesive layer includes the following components by mass: 0.5%-10% of nano-insulation coating, benzotriazine-based ultraviolet absorption 0.1% to 1% of adhesive, 30% to 50% of adhesive, 0.05% to 15% of curing agent, 30% to 40% of toluene and 3% to 20% of ethyl acetate.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the nano-insulation coating further includes antimony tin oxide nanoparticles (ATO), indium tin oxide nanoparticles (ITO), zinc oxide nanoparticles ( At least one of ZnO), vanadium pentoxide nanoparticles (V ₂ O ₅ ), and titanium dioxide nanoparticles (TiO ₂ ).

In the invention, cesium tungsten bronze nanoparticles can be used in combination with inorganic nanoparticles such as ATO, ITO, ZnO, V ₂ O ₅ , TiO ₂ , etc., so as to improve the cost performance of the solar film.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano solar film of the present invention, the anti-scratch and wear-resistant layer comprises the following components by mass percentage: 27% to 42% of scratch resistance agent, 25% to 25% of n-butanol 35%, 25% to 35% of toluene and 0.5% to 3% of photoinitiator.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the anti-scratch agent is a polyurethane-based anti-scratch agent or a polyacrylate-based anti-scratch agent; the photoinitiator is phenyl bis(2 , 4,6-trimethylbenzoyl) phosphine oxide.

The invention effectively improves the abrasion resistance and scratch resistance of the solar film by optimizing the components and proportions of the scratch-resistant and wear-resistant layer.

As a preferred embodiment of the anti-ultraviolet heat-insulating inorganic nano-solar film of the present invention, the release film is a PET release film with visible light transmittance greater than 90%, the first PET base film and the second PET base film The films are all PET base films with visible light transmittance greater than 90%.

The present invention also provides a method for preparing the above-mentioned anti-ultraviolet heat-insulating inorganic nano-solar film, which is characterized by comprising the following steps:

(1) prepare the release film, the first PET base film and the second PET base film;

(2) respectively preparing the mixture A for forming the anti-ultraviolet layer, the mixture B for forming the thermal insulation adhesive layer and the mixture C for forming the anti-scratch and wear-resistant layer;

(3) Coating mixed material C on one surface of the second PET base film, and obtaining an anti-scratch and wear-resistant layer through ultraviolet curing; coating mixed material B on the other surface of the second PET base film, at a temperature of 70 ℃ ℃～100℃, after standing for 2～5min, solidify to obtain the heat insulating adhesive layer; compound one surface of the first PET base film on the outer surface of the heat insulating adhesive layer, and coat the other surface of the first PET base film Mixed material A, at a temperature of 70 ℃ ~ 100 ℃, after standing for 2 ~ 5 minutes, curing to obtain an anti-ultraviolet layer, and then compounding the release film on the outer surface of the anti-ultraviolet layer, so as to obtain an anti-ultraviolet layer in which each layer is closely integrated Thermal Insulation Inorganic Nano Solar Film.

Compared with the prior art, the beneficial effects of the present invention are:

In the solar film of the invention, the heat-insulating coating containing cesium tungsten bronze nanoparticles is added to the heat-insulating adhesive layer, and the benzotriazine type ultraviolet absorber is added to the anti-ultraviolet layer. The rate is greater than 99%, the infrared blocking rate is 50% to 99%, and the visible light transmittance is 30% to 80%. After 600h aging test, the ultraviolet blocking rate and infrared blocking rate will not decrease, and the solar film will not bubbling and yellowing. The peel strength meets the requirements of the national standard.

The solar film of the present invention has a simple preparation process and is easy to operate. According to the size of the glass, the outer release film can be torn off and stuck on the glass surface, which can achieve the effect of anti-ultraviolet heat insulation and energy saving, and has a long service life.

Description of drawings

Fig. 1 is the structural schematic diagram of the anti-ultraviolet heat-insulating inorganic nano solar film of the present invention, in the figure, 1- release film, 2- anti-ultraviolet layer, 3- first PET base film, 4- heat insulating adhesive layer, 5- The second PET base film, 6-anti-scratch and wear-resistant layer.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used can be obtained from commercial sources unless otherwise specified.

Benzotriazole UV absorber: UV326, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole; UV-P, 2- (2'-Hydroxy5'-methylphenyl)benzotriazole; UV-327, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole azole; UV-234, 2-(2'-hydroxy-3', 5'bis(a,a-dimethylbenzyl)phenyl)benzotriazole; UV-320, 2-(2'-hydroxyl -3',5'-di-tert-butylphenyl)-benzotriazole.

Benzotriazine UV absorbers: UV-400, 2-[4-[2-hydroxy-3-tridecyloxypropyl]oxy]-2-hydroxyphenyl]-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-triazine and 2-[4-[2-hydroxy-3-dodecyloxypropyl]oxy]-2-hydroxyphenyl] -4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine mixture; UV-479A and UV-479B are a series of products of BASF Tinuvin479, which are synthetic hydroxyphenyl triazine oxazine (HPT) UV absorber.

Adhesive: BA5L (Nanjing Box New Material Technology Co., Ltd.).

Curing agent: BOX (Nanjing Box New Material Technology Co., Ltd.).

Anti-scratch agent: 4GU-T55 (Shanghai Huzheng Nano Technology Co., Ltd.), polyacrylate anti-scratch agent.

Photoinitiator: 819, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, whose structure is shown in formula I:

Example 1

As an embodiment of the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film described in this embodiment includes the following steps:

(1) prepare the release film, the first PET base film and the second PET base film;

The release film is a PET release film with a thickness of 23 microns, transparent, and light transmittance greater than 90%; prepare a first PET base film with a thickness of 38 microns; prepare a second PET base film with a thickness of 38 microns, and the first PET base film is prepared. The base film and the second PET base film are selected from transparent PET base films with a light transmittance greater than 90%.

(2) respectively preparing the mixture A for forming the anti-ultraviolet layer, the mixture B for forming the thermal insulation adhesive layer and the mixture C for forming the anti-scratch and wear-resistant layer;

The preparation method of the mixed material A for forming the anti-ultraviolet layer is:

The anti-ultraviolet layer comprises the following components by mass percentage: UV-326 0.3%, UV-479A 0.3%, adhesive BA5L 48%, curing agent BOX 0.4%, toluene 34% and ethyl acetate 17%;

Weigh the components according to the proportion, first mix the UV absorber with toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, stir for 5 minutes/2 times, and measure with a rotational viscometer The obtained viscosity was 3000 cps, and the mixed material A for forming an anti-ultraviolet layer was prepared, which was sealed for use after defoaming.

The preparation method of the mixed material B for forming the thermal insulation adhesive layer is:

The thermal insulation adhesive layer comprises the following components by mass percentage: nano thermal insulation coating containing nano cesium tungsten bronze 2%, UV-479A 0.3%, adhesive BA5L 40%, curing agent BOX 0.4%, toluene 38% and ethyl acetate Ester 19.3%, the nano thermal insulation coating includes cesium tungsten bronze nanoparticles with an average particle size of less than 40nm;

Weigh the components according to the proportion, first mix the UV absorber, toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, and stir for 5 minutes/2 times, and finally add the nano thermal insulation coating , Mix and stir for 5min/2 times, and store for later use after defoaming.

The preparation method of the mixed material C for forming the anti-scratch and wear-resistant layer is:

The anti-scratch and wear-resistant layer comprises the following components in mass percentage: polyacrylate anti-scratch agent 4GU-T5539.4%, n-butanol 29.55%, toluene 29.55% and photoinitiator 819 1.5%;

Weigh each component in proportion, first mix photoinitiator, toluene and n-butanol and stir for 5min, then add polyacrylate anti-scratch agent, mix and stir for 5min/2 times, and store for later use.

(3) As shown in FIG. 1 , the mixture material C is coated on one surface of the second PET base film 5, and the anti-scratch and wear-resistant layer 6 is obtained through ultraviolet light curing; on the other surface of the second PET base film 5 The coating mixture B is placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain a thermal insulation adhesive layer 4; The other surface of the first PET base film 3 is coated with the mixed material A, placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain an anti-ultraviolet layer 2, and then the release film 1 is compounded on the anti-ultraviolet layer 2. The outer surface of the film can be obtained to obtain an anti-ultraviolet heat-insulating inorganic nano-solar film in which each layer is closely attached as a whole.

In this embodiment, the benzotriazole type ultraviolet absorber is UV-326, and other benzotriazole type ultraviolet absorbers can also be used instead, such as UV-327, UV-P, UV-234, UV-320; The triazine UV absorber is UV-479A, which can also be replaced by other benzotriazine UV absorbers, such as UV-400 and UV-479B; the curing agent can also be replaced by the existing conventional curing agent; the adhesive can also be Choose an existing conventional adhesive product instead.

Example 2

The anti-ultraviolet heat-insulating inorganic nano-solar film and the preparation method thereof in this embodiment are basically the same as those in Embodiment 1, except that the anti-ultraviolet layer in this embodiment includes the following components by mass percentage: the anti-ultraviolet layer includes Components in the following mass percentages: UV-326 0.1%, UV-479A 0.5%, adhesive BA5L 48%, curing agent BOX 0.4%, toluene 34% and ethyl acetate 17%.

Example 3

The anti-ultraviolet heat-insulating inorganic nano-solar film and the preparation method thereof in this embodiment are basically the same as those in Embodiment 1, except that the anti-ultraviolet layer in this embodiment includes the following components by mass percentage: the anti-ultraviolet layer includes Components in the following mass percentages: UV-479A 0.6%, adhesive BA5L 48%, curing agent BOX 0.4%, toluene 34% and ethyl acetate 17%.

Example 4

As an embodiment of the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film described in this embodiment includes the following steps:

(1) prepare the release film, the first PET base film and the second PET base film;

The release film is a PET release film with a thickness of 23 microns, transparent, and light transmittance greater than 90%; prepare a first PET base film with a thickness of 38 microns; prepare a second PET base film with a thickness of 38 microns, and the first PET base film is prepared. The base film and the second PET base film are selected from transparent PET base films with a light transmittance greater than 90%.

(2) respectively preparing the mixture A for forming the anti-ultraviolet layer, the mixture B for forming the thermal insulation adhesive layer and the mixture C for forming the anti-scratch and wear-resistant layer;

The preparation method of the mixed material A for forming the anti-ultraviolet layer is:

The anti-ultraviolet layer comprises the following components by mass percentage: UV-326 0.05%, UV-479A 0.05%, adhesive BA5L 43.9%, curing agent BOX 1%, toluene 40% and ethyl acetate 15%;

Weigh the components according to the proportion, first mix the UV absorber, toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, stir for 5 minutes/2 times, and measure with a rotational viscometer The obtained viscosity was 3000 cps, and the mixed material A for forming an anti-ultraviolet layer was prepared, which was sealed for use after defoaming.

The preparation method of the mixed material B for forming the thermal insulation adhesive layer is:

The thermal insulation adhesive layer comprises the following components by mass percentage: nano thermal insulation coating containing nano cesium tungsten bronze 5%, UV-479A 0.5%, adhesive BA5L 38%, curing agent BOX 15%, toluene 38.5% and ethyl acetate Ester 3%, the nano thermal insulation coating includes cesium tungsten bronze nanoparticles and tin and antimony oxide nanoparticles with an average particle size of less than 40nm, and the mass ratio of cesium tungsten bronze nanoparticles and tin and antimony oxide nanoparticles is 1:1;

Weigh the components according to the proportion, first mix the UV absorber with toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, and stir for 5 minutes/2 times, and finally add the nano thermal insulation coating , Mix and stir for 5min/2 times, and store for later use after defoaming.

The preparation method of the mixed material C for forming the anti-scratch and wear-resistant layer is:

The anti-scratch and wear-resistant layer comprises the following components in mass percentage: polyacrylate anti-scratch agent 4GU-T5538%, n-butanol 25%, toluene 35% and photoinitiator 819 2%;

Weigh each component in proportion, first mix photoinitiator, toluene and n-butanol and stir for 5min, then add polyacrylate anti-scratch agent, mix and stir for 5min/2 times, and store for later use.

(3) As shown in FIG. 1 , the mixture material C is coated on one surface of the second PET base film 5, and the anti-scratch and wear-resistant layer 6 is obtained through ultraviolet light curing; on the other surface of the second PET base film 5 The coating mixture B is placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain a thermal insulation adhesive layer 4; The other surface of the first PET base film 3 is coated with the mixed material A, placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain an anti-ultraviolet layer 2, and then the release film 1 is compounded on the anti-ultraviolet layer 2. The outer surface of the film can be obtained to obtain an anti-ultraviolet heat-insulating inorganic nano-solar film in which each layer is closely attached as a whole.

Example 5

As an embodiment of the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film described in this embodiment includes the following steps:

(1) prepare the release film, the first PET base film and the second PET base film;

The release film is a PET release film with a thickness of 23 microns, transparent, and light transmittance greater than 90%; prepare a first PET base film with a thickness of 38 microns; prepare a second PET base film with a thickness of 38 microns, and the first PET base film is prepared. The base film and the second PET base film are selected from transparent PET base films with a light transmittance greater than 90%.

(2) respectively preparing the mixture A for forming the anti-ultraviolet layer, the mixture B for forming the thermal insulation adhesive layer and the mixture C for forming the anti-scratch and wear-resistant layer;

The preparation method of the mixed material A for forming the anti-ultraviolet layer is:

The anti-ultraviolet layer comprises the following components by mass percentage: UV-326 0.3%, UV-479A 0.7%, adhesive BA5L 55%, curing agent BOX 0.05%, toluene 25% and ethyl acetate 18.95%;

Weigh the components according to the proportion, first mix the UV absorber, toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, stir for 5 minutes/2 times, and measure with a rotational viscometer The obtained viscosity was 3000 cps, and the mixed material A for forming an anti-ultraviolet layer was prepared, which was sealed for use after defoaming.

The preparation method of the mixed material B for forming the thermal insulation adhesive layer is:

The thermal insulation adhesive layer comprises the following components by mass percentage: nano thermal insulation coating containing nano cesium tungsten bronze 10%, UV-479A 0.1%, adhesive BA5L 30%, curing agent BOX 9.9%, toluene 30% and ethyl acetate Ester 20%, the nano thermal insulation coating includes cesium tungsten bronze nanoparticles with an average particle size of less than 40nm;

Weigh the components according to the proportion, first mix the UV absorber with toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, and stir for 5 minutes/2 times, and finally add the nano thermal insulation coating , Mix and stir for 5min/2 times, and store for later use after defoaming.

The preparation method of the mixed material C for forming the anti-scratch and wear-resistant layer is:

The anti-scratch and wear-resistant layer comprises the following components in mass percentage: polyacrylate anti-scratch agent 4GU-T5537%, n-butanol 35%, toluene 25% and photoinitiator 819 3%;

Weigh each component in proportion, first mix photoinitiator, toluene and n-butanol and stir for 5min, then add polyacrylate anti-scratch agent, mix and stir for 5min/2 times, and store for later use.

(3) As shown in FIG. 1 , the mixture material C is coated on one surface of the second PET base film 5, and the anti-scratch and wear-resistant layer 6 is obtained through ultraviolet light curing; on the other surface of the second PET base film 5 The coating mixture B is placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain a thermal insulation adhesive layer 4; The other surface of the first PET base film 3 is coated with the mixed material A, placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain an anti-ultraviolet layer 2, and then the release film 1 is compounded on the anti-ultraviolet layer 2. The outer surface of the film can be obtained to obtain an anti-ultraviolet heat-insulating inorganic nano-solar film in which each layer is closely attached as a whole.

Example 6

As an embodiment of the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film of the present invention, the preparation method of the UV-resistant and heat-insulating inorganic nano-solar film described in this embodiment includes the following steps:

(1) prepare the release film, the first PET base film and the second PET base film;

The release film is a PET release film with a thickness of 23 microns, transparent, and light transmittance greater than 90%; prepare a first PET base film with a thickness of 38 microns; prepare a second PET base film with a thickness of 38 microns, and the first PET base film is prepared. The base film and the second PET base film are selected from transparent PET base films with a light transmittance greater than 90%.

(2) respectively preparing the mixture A for forming the anti-ultraviolet layer, the mixture B for forming the thermal insulation adhesive layer and the mixture C for forming the anti-scratch and wear-resistant layer;

The preparation method of the mixed material A for forming the anti-ultraviolet layer is:

The anti-ultraviolet layer comprises the following components by mass percentage: UV-326 0.3%, UV-479A 0.3%, adhesive BA5L 40%, curing agent BOX 0.4%, toluene 40% and ethyl acetate 19%;

Weigh the components according to the proportion, first mix the UV absorber, toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, stir for 5 minutes/2 times, and measure with a rotational viscometer The obtained viscosity was 3000 cps, and the mixed material A for forming an anti-ultraviolet layer was prepared, which was sealed for later use after defoaming.

The preparation method of the mixed material B for forming the thermal insulation adhesive layer is:

The thermal insulation adhesive layer comprises the following components by mass percentage: nano thermal insulation coating containing nano cesium tungsten bronze 0.5%, UV-479A 1%, adhesive BA5L 50%, curing agent BOX 0.05%, toluene 40% and ethyl acetate Ester 8.45%, the nano thermal insulation coating includes cesium tungsten bronze nanoparticles with an average particle size of less than 40nm;

Weigh the components according to the proportion, first mix the UV absorber with toluene and ethyl acetate and stir for 5 minutes, then add the curing agent and mix evenly, then add the adhesive and mix evenly, and stir for 5 minutes/2 times, and finally add the nano thermal insulation coating , Mix and stir for 5min/2 times, and store for later use after defoaming.

The preparation method of the mixed material C for forming the anti-scratch and wear-resistant layer is:

The anti-scratch and wear-resistant layer comprises the following components in mass percentage: polyacrylate anti-scratch agent 4GU-T5542%, n-butanol 27.5%, toluene 30% and photoinitiator 819 0.5%;

Weigh each component in proportion, first mix photoinitiator, toluene and n-butanol and stir for 5min, then add polyacrylate anti-scratch agent, mix and stir for 5min/2 times, and store for later use.

(3) As shown in FIG. 1 , the mixture material C is coated on one surface of the second PET base film 5, and the anti-scratch and wear-resistant layer 6 is obtained through ultraviolet light curing; on the other surface of the second PET base film 5 The coating mixture B is placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain a thermal insulation adhesive layer 4; The other surface of the first PET base film 3 is coated with the mixed material A, placed at a temperature of 70°C to 100°C for 2 to 5 minutes, and then cured to obtain an anti-ultraviolet layer 2, and then the release film 1 is compounded on the anti-ultraviolet layer 2. The outer surface of the film can be obtained to obtain an anti-ultraviolet heat-insulating inorganic nano-solar film in which each layer is closely attached as a whole.

Comparative Example 1

The anti-ultraviolet heat-insulating inorganic nano-solar film of this comparative example and its preparation method are basically the same as those in Example 1, except that the anti-ultraviolet layer in this comparative example includes the following components by mass: UV-326 0.6%, Adhesive BA5L 48%, hardener BOX 0.4%, toluene 34% and ethyl acetate 17%.

Comparative Example 2

The anti-ultraviolet heat-insulating inorganic nano-solar film of this comparative example and its preparation method are basically the same as those of Comparative Example 1, the difference is that the heat-insulating adhesive layer of this comparative example includes the following components in mass percentage: containing nano-cesium tungsten bronze The nano thermal insulation coating 2%, UV-326 0.3%, adhesive BA5L 40%, curing agent BOX 0.4%, toluene 38% and ethyl acetate 19.3%, the nano thermal insulation coating includes cesium tungsten with an average particle size of less than 40nm Bronze Nanoparticles.

The properties of the anti-ultraviolet heat-insulating inorganic nano-solar films prepared in Examples 1-6 and Comparative Examples 1-2 were tested according to the following methods, and the results are shown in Table 1:

1. Optical performance test: The solar film transmittance tester (model LS182) produced by Shenzhen Linshang Technology Co., Ltd. is used, and it is carried out according to the standard method of ASTM D1003;

2. Peel strength test: test with reference to the national standard GB31849-2015;

3. Abrasion resistance test: The abrasion tester (model) produced by Dongguan Lixian Instrument Technology Co., Ltd. is used to test with reference to the national standard GB31849-2015;

4. Aging resistance test: The xenon lamp weather resistance test box (air-cooled) (model HZ-2011) produced by Dongguan Lixian Instrument Technology Co., Ltd. is used, and the test is carried out with reference to the national standard GB31849-2015.

Table 1

As can be seen from the test results in Table 1, the results of Comparative Examples and Comparative Examples 1-2, when the amount of benzotriazole UV absorber added is large (greater than 0.4wt%), due to its compatibility with the adhesive The property is not very good. With the prolongation of use time, it is easy to precipitate and gather in the solar film layer to form dots or snowflakes, resulting in a decrease in the UV blocking rate and an increase in haze, which affects the use effect. When its addition amount is less than 0.4wt%, this phenomenon does not occur.

To sum up, the anti-ultraviolet and heat-insulating inorganic nano-solar film of the present invention has excellent anti-scratch performance, can effectively block infrared radiation to achieve the effect of saving heat and heat, the anti-ultraviolet effect reaches more than 99%, and is resistant to aging. After 600h of irradiation in the test device, various performance indicators remained stable, and the UV absorber in the solar film had good compatibility with the adhesive, which did not affect the anti-ultraviolet heat insulation performance of the solar film.

The preparation method of the anti-ultraviolet heat-insulating inorganic nano solar film of the present invention is simple and easy to operate; when in use, according to the size of the glass, tear off the outer release film and stick it on the glass surface, and the solar film has good anti-ultraviolet heat insulation and energy saving. effect, and the service life is longer.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. An anti-ultraviolet heat-insulating inorganic nano solar film is characterized by comprising a release film, an anti-ultraviolet layer, a first PET base film, a heat-insulating glue layer, a second PET base film and an anti-scratching wear-resistant layer which are sequentially and closely adhered into a whole;

the heat insulation glue layer contains a nano heat insulation coating, and the nano heat insulation coating comprises cesium tungsten bronze nanoparticles with the average particle size of less than 40 nm;

the ultraviolet-resistant layer contains the phentriazine ultraviolet absorbent, and the mass percentage of the phentriazine ultraviolet absorbent in the ultraviolet-resistant layer is not more than 1%.

2. The ultraviolet-resistant heat-insulating inorganic nano solar film according to claim 1, wherein the ultraviolet-resistant layer further contains a benzotriazole ultraviolet absorbent, and the sum of the mass percentages of the benzotriazole ultraviolet absorbent and the benzotriazole ultraviolet absorbent in the ultraviolet-resistant layer is not more than 1%.

3. The ultraviolet-resistant heat-insulating inorganic nano solar film according to claim 2, wherein the ultraviolet-resistant layer comprises the following components in percentage by mass: 0.1-1% of a mixture of benzotriazole ultraviolet absorbent and benzo triazine ultraviolet absorbent, 40-55% of adhesive, 0.05-1% of curing agent, 25-40% of toluene and 15-20% of ethyl acetate.

4. The ultraviolet resistant and heat insulating inorganic nano solar film according to claim 2 or 3, wherein the benzotriazole ultraviolet absorber is at least one of 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy 5' -methylphenyl) benzotriazole, 2- (2' -hydroxy-3 ', 5' -diterbutyl phenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ', 5' bis (a, a-dimethylbenzyl) phenyl) benzotriazole, 2- (2' -hydroxy-3 ', 5' -di-tert-butylphenyl) -benzotriazole; the phentriazine ultraviolet absorbent is a hydroxyphenyl triazine compound, and preferably, the phentriazine ultraviolet absorbent is at least one of UV-400 and UV-479A, UV-479B.

5. The ultraviolet-resistant heat-insulating inorganic nano solar film according to claim 1, wherein the heat-insulating glue layer further contains a phentriazine ultraviolet absorbent, and preferably comprises the following components in percentage by mass: 0.5-10% of nano heat-insulating coating, 0.1-1% of phentriazine ultraviolet absorbent, 30-50% of adhesive, 0.05-15% of curing agent, 30-40% of toluene and 3-20% of ethyl acetate.

6. The ultraviolet-resistant thermal-insulating inorganic nano solar film according to claim 1 or 5, wherein the nano thermal-insulating coating further comprises at least one of tin antimony oxide nanoparticles, indium tin oxide nanoparticles, zinc oxide nanoparticles, vanadium pentoxide nanoparticles and titanium dioxide nanoparticles.

7. The ultraviolet-resistant heat-insulating inorganic nano solar film according to claim 1, wherein the scratch-resistant wear-resistant layer comprises the following components in percentage by mass: 27-42% of scratch-resistant agent, 25-35% of n-butanol, 25-35% of toluene and 0.5-3% of photoinitiator.

8. The ultraviolet-resistant thermal-insulating inorganic nano solar film according to claim 7, wherein the scratch-resistant agent is a polyurethane scratch-resistant agent or a polyacrylate scratch-resistant agent; the photoinitiator is phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

9. The ultraviolet-resistant heat-insulating inorganic nano solar film according to claim 1, wherein the release film is a PET release film with visible light transmittance of more than 90%, and the first PET base film and the second PET base film are both PET base films with visible light transmittance of more than 90%.

10. The preparation method of the ultraviolet-resistant heat-insulating inorganic nano solar film according to any one of claims 1 to 9, characterized by comprising the following steps:

(1) preparing a release film, a first PET base film and a second PET base film;

(2) respectively preparing a mixed material A for forming an ultraviolet-resistant layer, a mixed material B for forming a heat-insulating glue layer and a mixed material C for forming an anti-scratching wear-resistant layer;

(3) coating the mixed material C on one surface of the second PET base film, and performing ultraviolet curing to obtain an anti-scratch wear-resistant layer; coating the mixed material B on the other surface of the second PET base film, standing at the temperature of 70-100 ℃ for 2-5 min, and curing to obtain a heat insulation glue layer; compounding one surface of a first PET base film on the outer surface of a heat insulation glue layer, coating a mixed material A on the other surface of the first PET base film, standing at the temperature of 70-100 ℃ for 2-5 min, curing to obtain an ultraviolet-resistant layer, and compounding a release film on the outer surface of the ultraviolet-resistant layer, so that the ultraviolet-resistant heat insulation inorganic nano solar film with the layers tightly adhered into a whole is obtained.

Images