A light-shielding glass film and a method for manufacturing the same

Abstract

The application relates to a light-shielding glass film and a preparation method thereof, and belongs to the film pasting technology, wherein the light-shielding glass film takes a polyester film as a base material, an outer side of the base material is provided with a light-shielding layer, the light-shielding layer comprises the following components in parts by weight: 40-50 parts of a hydroxyl acrylic resin, 20-25 parts of polycarbonate dihydric alcohol coated carbon black, 10-18 parts of toluene diisocyanate, 30-60 parts of toluene and 0.1-1 part of a catalyst. The polycarbonate dihydric alcohol coated carbon black is prepared to improve the compatibility of the carbon black and the hydroxyl acrylic resin, increase the steric hindrance of the carbon black, improve the dispersivity of the carbon black in the hydroxyl acrylic resin, and further improve the light-shielding effect of the light-shielding glass film.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of film pasting, and particularly relates to a light-shielding glass film and a preparation method thereof. BACKGROUND

[0002] The glass film refers to a thin film product used for pasting on the surface of automobile glass, building glass or other glass, which can protect the glass from being scratched by external objects, keep the glass clean and prolong the service life of the glass. The light-shielding glass film is usually provided with a black light-shielding layer on one side of the glass film substrate, which mainly shields light and blocks the transmission of heat, and can also protect the privacy in the room or the car.

[0003] In the prior art, the black light-shielding layer is mainly composed of a resin mixture containing a light-shielding agent (such as carbon black, titanium oxide, etc.). However, since the carbon black particles have few polar groups on the surface, the surface is inert, so when added to the resin, there are poor compatibility with the resin and poor particle dispersion, which affects the light-shielding effect of the glass film, and thus needs to be improved. SUMMARY

[0004] In view of the above, in order to overcome at least some of the defects of the prior art, the application provides a light-shielding glass film and a preparation method thereof.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the application is as follows:

[0006] The application provides a light-shielding glass film, which takes a polyester film as a substrate, and a light-shielding layer is arranged on the outer side of the substrate, and the light-shielding layer comprises the following components in parts by weight: 40-50 parts of hydroxy acrylic resin, 20-25 parts of polycarbonate dihydric alcohol coated carbon black, 10-18 parts of toluene diisocyanate, 30-60 parts of toluene and 0.1-1 part of a catalyst.

[0007] In some embodiments, the light-shielding layer comprises the following components in parts by weight: 40-42 parts of hydroxy acrylic resin, 20-22 parts of polycarbonate dihydric alcohol coated carbon black, 15-18 parts of toluene diisocyanate, 30-40 parts of toluene and 0.5-1 part of a catalyst.

[0008] In some embodiments, the catalyst is one of dibutyltin dilaurate, stannous octoate and bismuth isooctoate.

[0009] The application also provides a preparation method of the light-shielding glass film, which comprises the following steps:

[0010] The polycarbonate dihydric alcohol coated carbon black is added into toluene, toluene diisocyanate and a catalyst are added, and reaction is carried out at 80-100 DEG C for 20-40 min, and then rotary evaporation is carried out after the reaction is completed.

[0011] The hydroxyl acrylic resin is added into toluene, the rotary evaporation product is added, and after stirring uniformly, it is coated onto a substrate, and after curing, an anti-glare glass film is obtained.

[0012] In some embodiments, the preparation method of the polycarbonate diol coated carbon black comprises:

[0013] The carbon black is added into an oxidizing agent, and reacted at 70-100 DEG C for 10-20 hours, washed, dried, and an oxidized carbon black is obtained;

[0014] The oxidized carbon black, polycarbonate diol and condensing agent are mixed, and reacted at 50-80 DEG C for 5-10 hours, and a polycarbonate diol coated carbon black is obtained.

[0015] In some embodiments, the oxidizing agent is nitric acid or hydrogen peroxide.

[0016] In some embodiments, the carbon black is added into the oxidizing agent in an amount of 0.1-0.2 g / mL.

[0017] In some embodiments, the condensing agent is dicyclohexyl carbodiimide or diisopropyl carbodiimide.

[0018] In some embodiments, the mixing ratio of the oxidized carbon black, polycarbonate diol and condensing agent is 20:(1-5):(0.1-0.5).

[0019] The present application has the following beneficial effects:

[0020] By preparing the polycarbonate diol coated carbon black, the compatibility of the carbon black and the hydroxyl acrylic resin is improved, and the steric hindrance of the carbon black is increased, thereby improving the dispersibility of the carbon black in the hydroxyl acrylic resin, and further improving the anti-glare effect of the anti-glare glass film; at the same time, the toluene diisocyanate is used as a connecting bridge, the hydroxyl acrylic resin and the polycarbonate diol coated carbon black are subjected to a curing crosslinking reaction, the crosslinking density of the hydroxyl acrylic resin is improved, and the surface hardness of the anti-glare glass film is improved. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Also, any method and material similar or equivalent to those described herein can be used in the practice of the present application. The preferred materials and methods are described herein, by way of example only, and without limitation.

[0023] In order to solve the problems existing in the prior art mentioned in the background, the first aspect of the embodiment of the present application provides a shading glass film, which is prepared by using a polyester film as a substrate, and an shading layer is arranged on the outer side of the substrate, and the shading layer comprises the following components in parts by weight: 40-50 parts of hydroxyl acrylic resin, 20-25 parts of polycarbonate dihydric alcohol coated carbon black, 10-18 parts of toluene diisocyanate, 30-60 parts of toluene and 0.1-1 part of a catalyst.

[0024] Since the carbon black particles have few polar groups on the surface, the surface of the carbon black particles is inert, and when the carbon black particles are added to the resin, the carbon black particles have poor compatibility with the resin and poor particle dispersibility, which affects the shading effect of the glass film. By grafting polycarbonate dihydric alcohol on the surface of the carbon black particles, the dispersibility of the carbon black particles in the hydroxyl acrylic resin is improved, and the steric hindrance of the carbon black particles is increased, so that the dispersibility of the carbon black particles in the hydroxyl acrylic resin is improved, and the shading effect of the shading glass film is improved.

[0025] The hydroxyl acrylic resin is a thermosetting acrylic resin containing a hydroxyl functional group, which has good weather resistance, and can maintain the gloss and color stability of the film for a long time even if it is used outdoors for a long time. In addition, the hydroxyl groups in the molecule can crosslink with isocyanate, and the polycarbonate dihydric alcohol coated carbon black can be cured and crosslinked with the hydroxyl acrylic resin by using toluene diisocyanate as a connecting bridge, so that the crosslinking density of the hydroxyl acrylic resin is improved, and the surface hardness of the shading glass film is improved.

[0026] Preferably, the shading layer comprises the following components in parts by weight: 40-42 parts of hydroxyl acrylic resin, 20-22 parts of polycarbonate dihydric alcohol coated carbon black, 15-18 parts of toluene diisocyanate, 30-40 parts of toluene and 0.5-1 part of a catalyst. Experiments show that the shading glass film has high surface hardness under the above weight parts.

[0027] Preferably, the catalyst is one of dibutyltin dilaurate, stannous octoate and bismuth isooctoate. The catalyst can improve the reaction efficiency of the hydroxyl groups with the isocyanate, and the dibutyltin dilaurate, stannous octoate and bismuth isooctoate have high catalytic activity and stability.

[0028] The second aspect of the embodiment of the present application provides a preparation method of a shading glass film, which comprises the following steps:

[0029] Take polycarbonate diol coated carbon black into toluene, add toluene diisocyanate and catalyst, 80-100℃ reaction for 20-40min, after the reaction is completed, spin evaporation is carried out;

[0030] Take hydroxy acrylic acid resin into toluene, add spin evaporation product, stir uniformly, then coat on the substrate, and after curing, the sunscreen glass film is obtained.

[0031] Toluene diisocyanate can react with polycarbonate diol on the surface of carbon black, thereby introducing isocyanate groups on the surface of carbon black. Carbon black containing isocyanate groups on the surface can be cured and crosslinked with hydroxy acrylic acid resin, thereby preparing a sunscreen layer with high crosslinking density, and further improving the surface hardness of the sunscreen glass film.

[0032] In some embodiments, the preparation method of polycarbonate diol coated carbon black comprises:

[0033] Take carbon black into oxidant, 70-100℃ reaction for 10-20h, wash, dry, and obtain oxidized carbon black;

[0034] Mix oxidized carbon black, polycarbonate diol and condensing agent, 50-80℃ reaction for 5-10h, and obtain polycarbonate diol coated carbon black.

[0035] Oxidation modification of the surface of carbon black by oxidant can form a large number of carboxyl groups on the surface of carbon black. Then, under the condition of condensing agent, the carboxyl groups on the surface of carbon black can react with polycarbonate diol, thereby grafting polycarbonate diol to the surface of carbon black.

[0036] Among them, the oxidant is nitric acid or hydrogen peroxide. Preferably, the addition amount of carbon black in the oxidant is 0.1-0.2g / mL. If the addition amount of carbon black in the oxidant is too low, the collision opportunity of oxidant molecules with carbon black particles will be reduced, which will reduce the reaction rate. If the addition amount of carbon black in the oxidant is too high, the reaction efficiency will be reduced due to the agglomeration of carbon black particles. Therefore, the addition amount of carbon black in the oxidant needs to be set to 0.1-0.2g / mL.

[0037] Preferably, the condensing agent is dicyclohexyl carbodiimide or diisopropyl carbodiimide. Under the action of dicyclohexyl carbodiimide or diisopropyl carbodiimide, the carboxyl groups on the surface of oxidized carbon black will easily react with the hydroxyl groups of polycarbonate diol, thereby grafting polycarbonate diol to the surface of carbon black.

[0038] Preferably, the mixing ratio of the oxidized carbon black, the polycarbonate diol and the condensing agent is 20:(1-5):(0.1-0.5). By setting the mixing ratio of the oxidized carbon black, the polycarbonate diol and the condensing agent to 20:(1-5):(0.1-0.5), the surface of the oxidized carbon black can be fully grafted with the polycarbonate diol, while avoiding waste due to excessive addition.

[0039] The application will be further described in the following specific examples.

[0040] The experimental methods in the following examples are all conventional methods unless otherwise specified; the experimental materials used in the following examples are all commercially available unless otherwise specified.

[0041] Example 1

[0042] Take carbon black and add it to nitric acid, the addition amount of carbon black in nitric acid is 0.1 g / mL, react at 70°C for 10 h, wash, dry, and obtain oxidized carbon black;

[0043] Mix the oxidized carbon black, the polycarbonate diol and dicyclohexyl carbodiimide in a ratio of 20:1:0.1, react at 50°C for 5 h, and obtain polycarbonate diol coated carbon black;

[0044] Take 20 parts of polycarbonate diol coated carbon black and add it to 15 parts of toluene, add 10 parts of toluene diisocyanate and 0.1 part of dibutyltin dilaurate, react at 80°C for 20 min, and perform rotary evaporation after the reaction is completed;

[0045] Take 40 parts of hydroxyl acrylic resin and add it to 15 parts of toluene, add the rotary evaporation product, stir uniformly, and coat it onto a substrate, and obtain a sun-proof glass film after curing.

[0046] Example 2

[0047] Take carbon black and add it to hydrogen peroxide, the addition amount of carbon black in hydrogen peroxide is 0.2 g / mL, react at 100°C for 20 h, wash, dry, and obtain oxidized carbon black;

[0048] Mix the oxidized carbon black, the polycarbonate diol and diisopropyl carbodiimide in a ratio of 20:5:0.5, react at 80°C for 10 h, and obtain polycarbonate diol coated carbon black;

[0049] Take 20 parts of polycarbonate diol coated carbon black and add it to 15 parts of toluene, add 10 parts of toluene diisocyanate and 0.1 part of stannous octoate, react at 100°C for 40 min, and perform rotary evaporation after the reaction is completed;

[0050] Take 50 parts of hydroxyl acrylic resin and add it to 30 parts of toluene, add the rotary evaporation product, stir uniformly, and coat it onto a substrate, and obtain a sun-proof glass film after curing.

[0051] Example 3

[0052] The preparation of polycarbonate diol coated carbon black is consistent with Example 1, the difference is that the preparation of the light shielding layer includes the following steps:

[0053] Take 21 parts of polycarbonate diol coated carbon black into 15 parts of toluene, add 15 parts of toluene diisocyanate and 0.5 parts of dibutyltin dilaurate, react at 80°C for 20 min, and then perform rotary evaporation after the reaction is completed;

[0054] Take 41 parts of hydroxy acrylic resin into 20 parts of toluene, add the rotary evaporation product, stir uniformly, and then coat onto the substrate, and obtain the light shielding glass film after curing.

[0055] Example 4

[0056] The preparation of polycarbonate diol coated carbon black is consistent with Example 1, the difference is that the preparation of the light shielding layer includes the following steps:

[0057] Take 22 parts of polycarbonate diol coated carbon black into 15 parts of toluene, add 18 parts of toluene diisocyanate and 1 part of dibutyltin dilaurate, react at 80°C for 20 min, and then perform rotary evaporation after the reaction is completed;

[0058] Take 42 parts of hydroxy acrylic resin into 25 parts of toluene, add the rotary evaporation product, stir uniformly, and then coat onto the substrate, and obtain the light shielding glass film after curing.

[0059] Example 5

[0060] The preparation of polycarbonate diol coated carbon black is consistent with Example 1, the difference is that the preparation of the light shielding layer includes the following steps:

[0061] Take 23 parts of polycarbonate diol coated carbon black into 20 parts of toluene, add 12 parts of toluene diisocyanate and 0.2 parts of dibutyltin dilaurate, react at 80°C for 20 min, and then perform rotary evaporation after the reaction is completed;

[0062] Take 45 parts of hydroxy acrylic resin into 30 parts of toluene, add the rotary evaporation product, stir uniformly, and then coat onto the substrate, and obtain the light shielding glass film after curing.

[0063] Example 6

[0064] The preparation of polycarbonate diol coated carbon black is consistent with Example 1, the difference is that the preparation of the light shielding layer includes the following steps:

[0065] Take 24 parts of polycarbonate diol coated carbon black into 30 parts of toluene, add 13 parts of toluene diisocyanate and 0.3 parts of dibutyltin dilaurate, react at 80°C for 20 min, and then perform rotary evaporation after the reaction is completed;

[0066] Take 47 parts of hydroxy acrylic resin into 30 parts of toluene, add the rotary evaporation product, stir evenly, then coat on the substrate, and get the sunscreen glass film after curing.

[0067] Example 7

[0068] The preparation of polycarbonate diol coated carbon black is consistent with Example 1, except that the preparation of the sunscreen layer includes the following steps:

[0069] Take 25 parts of polycarbonate diol coated carbon black into 30 parts of toluene, add 14 parts of toluene diisocyanate and 0.4 parts of dibutyltin dilaurate, and react at 80℃ for 20min. After the reaction is completed, rotary evaporation is carried out;

[0070] Take 50 parts of hydroxy acrylic resin into 30 parts of toluene, add the rotary evaporation product, stir evenly, then coat on the substrate, and get the sunscreen glass film after curing.

[0071] Comparative Example 1

[0072] Consistent with Example 1, except that carbon black is used instead of polycarbonate diol coated carbon black.

[0073] The sunscreen glass film prepared in Examples 1-7 and Comparative Example 1 is tested, and the test content is as follows:

[0074] Sunscreen test:

[0075] UH4150 type ultraviolet visible near infrared spectrophotometer is used, with air as the background, to test the sunscreen property of the sunscreen glass film. The wavelength range for visible light transmittance test is 380-780nm, the wavelength range for ultraviolet barrier rate test is 280-400nm, and the wavelength range for infrared barrier rate test is 780-2500nm. The scanning speed is 600nm / min, and the test results are shown in Table 1.

[0076] Table 1

[0077] Visible light transmittance (%) Ultraviolet blocking rate (%) Infrared blocking rate (%) Example 1 60.3％ 99.5％ 94.5％ Example 2 62.5％ 99.3％ 93.1％ Example 3 61.1％ 99.6％ 94.7％ Example 4 63.5％ 99.7％ 94.8％ Example 5 63.2％ 99.2％ 94.1％ Example 6 63.8％ 99.1％ 93.8％ Example 7 64.5％ 99.1％ 93.7％ Comparative Example 1 68.4％ 90.4％ 81.3％

[0078] As can be seen from Table 1, the visible light transmittance of Examples 1-7 and Comparative Example 1 is more than 60%, at the same time, the ultraviolet barrier rate and infrared barrier rate of Example 1 are greatly improved compared with Comparative Example 1. Therefore, using polycarbonate diol coated carbon black can improve the sunscreen property of the film.

[0079] Surface hardness test:

[0080] The pencil hardness tester was used to test the film. The film was flatly pasted on the glass. Different hardness pencils were used to draw on the surface. The hardness of the pencil was gradually increased. The highest pencil hardness without causing scratches was recorded. The test results are shown in Table 2.

[0081] Table 2

[0082] Surface hardness Example 1 6H Example 2 5H Example 3 6H Example 4 6H Example 5 5H Example 6 5H Example 7 5H Comparative Example 1 3H

[0083] As can be seen from Table 2, the surface hardness of Example 1 is greatly improved compared to Comparative Example 1. Therefore, coating carbon black with carbonate diols can improve the surface hardness of the film, thereby enhancing the wear resistance of the film, increasing the service life of the film, and the surface hardness of Example 1, Example 3 and Example 4 is higher than that of other examples.

[0084] The above examples are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application. They should be covered in the protection scope of the present application.

Claims

1. A light-blocking glass film, characterized in that, Using polyester film as a substrate, a light-shielding layer is provided on the outer side of the substrate. The light-shielding layer comprises the following components in parts by weight: 40-50 parts of hydroxyl acrylic resin, 20-25 parts of polycarbonate diol-coated carbon black, 10-18 parts of toluene diisocyanate, 30-60 parts of toluene, and 0.1-1 parts of catalyst. The method for preparing the polycarbonate diol-coated carbon black includes: Add carbon black to an oxidant and react at 70℃-100℃ for 10-20 hours. Wash and dry to obtain carbon black oxide. After mixing carbon black oxide, polycarbonate diol and condensing agent, react at 50℃-80℃ for 5h-10h to obtain polycarbonate diol coated carbon black. The ratio of the carbon black oxide, polycarbonate diol and condensing agent is 20:(1-5):(0.1-0.5).

2. The light-shielding glass film according to claim 1, characterized in that, The light-shielding layer comprises the following components in parts by weight: 40-42 parts of hydroxyl acrylic resin, 20-22 parts of polycarbonate diol-coated carbon black, 15-18 parts of toluene diisocyanate, 30-40 parts of toluene, and 0.5-1 parts of catalyst.

3. The light-shielding glass film according to claim 1, characterized in that, The catalyst is one of dibutyltin dilaurate, stannous octoate, and bismuth isooctanoate.

4. The light-shielding glass film according to claim 1, characterized in that, The oxidant is nitric acid or hydrogen peroxide.

5. The light-shielding glass film according to claim 1, characterized in that, The amount of carbon black added to the oxidant is 0.1 g / mL to 0.2 g / mL.

6. The light-shielding glass film according to claim 1, characterized in that, The condensing agent is dicyclohexylcarbodiimide or diisopropylcarbodiimide.

7. The method for preparing the light-shielding glass film according to claim 1, characterized in that, include: Polycarbonate diol-coated carbon black was added to toluene, along with toluene diisocyanate and a catalyst. The reaction was carried out at 80℃-100℃ for 20-40 minutes. After the reaction was completed, rotary evaporation was performed. Hydroxy acrylic resin was added to toluene, followed by rotary evaporation product. After stirring evenly, the mixture was coated onto a substrate and cured to obtain a light-shielding glass film.