Shading glass film and preparation method thereof

Abstract

The invention relates to a shading glass film and a preparation method thereof, and belongs to a film pasting technology. The shading glass film takes a polyester film as a base material, and a shading layer is arranged on the outer side of the base material; the shading layer is prepared from the following components in parts by weight: 40 to 50 parts of hydroxy acrylic resin, 20 to 25 parts of polycarbonate diol coated carbon black, 10 to 18 parts of toluene diisocynate, 30 to 60 parts of toluene and 0.1 to 1 part of catalyst. The polycarbonate diol coated carbon black is prepared to improve the compatibility of the carbon black and the hydroxy acrylic resin and increase the steric hindrance of the carbon black, so that the dispersity of the carbon black in the hydroxy acrylic resin is improved, and the shading effect of the shading glass film is further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of film laminating, and particularly relates to a light-shielding glass film and a preparation method thereof. Background Art

[0002] A glass film refers to a relatively thin film product pasted on the surface of automotive glass, architectural glass or other glass, which can protect the glass from being scratched by external objects, keep the glass clean and improve the service life of the glass. A light-shielding glass film usually has a black light-shielding layer on one side of the glass film substrate, and its main functions are to block light, block the transfer of heat, and protect the privacy indoors or in the car at the same time.

[0003] In the prior art, the black light-shielding layer is mainly composed of a resin mixture containing light-shielding agents (such as carbon black, titanium oxide, etc.). However, since there are very few polar groups on the surface of carbon black particles, their surface shows inertness. Therefore, when added to the resin, there are disadvantages such as poor compatibility with the resin and poor particle dispersibility, which affect the light-shielding effect of the glass film. Therefore, it needs to be improved. Summary of the Invention

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

[0005] In order to achieve the above object, the technical solutions adopted by the present invention are as follows:

[0006] The present invention provides a light-shielding glass film, which uses a polyester film as a substrate, and a light-shielding layer is provided on the outer side of the substrate. The light-shielding layer includes the following components in parts by weight: 40-50 parts of hydroxy 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 part of catalyst.

[0007] In some embodiments, the light-shielding layer includes the following components in parts by weight: 40-42 parts of hydroxy 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 part of catalyst.

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

[0009] The present invention also provides a preparation method of a light-shielding glass film, including:

[0010] Take polycarbonate diol-coated carbon black and add it to toluene, add toluene diisocyanate and catalyst, react at 80°C - 100°C for 20 min - 40 min, and perform rotary evaporation after the reaction ends;

[0011] Take hydroxy acrylic resin and add it to toluene. Add the rotary evaporation product. After stirring evenly, coat it onto the substrate and cure to obtain a light-shielding glass film.

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

[0013] Take carbon black and add it to an oxidizing agent. React at 70 °C - 100 °C for 10 h - 20 h, wash, and dry to obtain oxidized carbon black;

[0014] After mixing the oxidized carbon black, polycarbonate diol, and condensing agent, react at 50 °C - 80 °C for 5 h - 10 h to obtain polycarbonate diol-coated carbon black.

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

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

[0017] In some embodiments, the condensing agent is dicyclohexylcarbodiimide or diisopropylcarbodiimide.

[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 beneficial effects achieved by the present invention are as follows:

[0020] By preparing polycarbonate diol-coated carbon black to improve the compatibility between carbon black and hydroxy acrylic resin and increase the steric hindrance of carbon black, thereby improving the dispersibility of carbon black in hydroxy acrylic resin and further improving the light-shielding effect of the light-shielding glass film; meanwhile, using toluene diisocyanate as a connecting bridge to carry out a curing crosslinking reaction between hydroxy acrylic resin and polycarbonate diol-coated carbon black can increase the crosslinking density of hydroxy acrylic resin, thereby improving the surface hardness of the light-shielding glass film. Specific Embodiments

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments; based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0022] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred implementation methods and materials described in the text are for demonstration purposes only and do not limit the content of this application.

[0023] In view of the deficiencies in the prior art mentioned in the background art, the first aspect of the embodiment of the present invention proposes a light-shielding glass film. The polyester film is used as the substrate, and a light-shielding layer is provided on the outer side of the substrate. The light-shielding layer includes the following components in parts by weight: 40-50 parts of hydroxy 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 part of catalyst.

[0024] Since carbon black particles have very few polar groups on their surfaces, resulting in an inert surface, when added to the resin, there are disadvantages such as poor compatibility with the resin and poor particle dispersibility, which affect the light-shielding effect of the glass film. By grafting polycarbonate diol on the surface of carbon black, the dispersibility of carbon black in hydroxy acrylic resin can be improved, and the steric hindrance of carbon black can be increased, thereby improving the dispersibility of carbon black in hydroxy acrylic resin and further improving the light-shielding effect of the light-shielding glass film.

[0025] Hydroxy acrylic resin, as a thermosetting acrylic resin containing hydroxy functional groups, has good weather resistance and can still maintain the gloss and color stability of the film during long-term outdoor use. Moreover, the hydroxy groups in its molecules can undergo a cross-linking reaction with isocyanate. Through toluene diisocyanate as a connecting bridge, polycarbonate diol-coated carbon black can be cured and cross-linked with hydroxy acrylic resin, thereby increasing the cross-linking density of hydroxy acrylic resin and further improving the surface hardness of the light-shielding glass film.

[0026] Preferably, the light-shielding layer includes the following components in parts by weight: 40-42 parts of hydroxy 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 part of catalyst. Experiments show that under the above parts by weight, the light-shielding glass film has a high surface hardness.

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

[0028] The second aspect of the embodiment of the present invention proposes a preparation method of a light-shielding glass film, including:

[0029] Take polycarbonate diol-coated carbon black, add it to toluene, add toluene diisocyanate and a catalyst, and react at 80°C - 100°C for 20 min - 40 min. After the reaction is completed, perform rotary evaporation;

[0030] Take hydroxy acrylic resin, add it to toluene, add the rotary evaporation product, stir evenly and then coat it on a substrate. After curing, a light-shielding glass film is obtained.

[0031] Toluene diisocyanate can react with the 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 cure and crosslink with hydroxy acrylic resin, thereby preparing a light-shielding layer with a relatively high crosslinking density, and further improving the surface hardness of the light-shielding glass film.

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

[0033] Take carbon black, add it to an oxidant, react at 70°C - 100°C for 10 h - 20 h, wash and dry to obtain oxidized carbon black;

[0034] After mixing oxidized carbon black, polycarbonate diol and a condensing agent, react at 50°C - 80°C for 5 h - 10 h to obtain polycarbonate diol-coated carbon black.

[0035] By oxidatively modifying the surface of carbon black with an oxidant, a large number of carboxyl groups can be formed on the surface of carbon black. Then, under the condition of a condensing agent, the carboxyl groups on the surface of carbon black can undergo a condensation reaction with polycarbonate diol, thereby grafting polycarbonate diol onto 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 g / mL - 0.2 g / mL. If the addition amount of carbon black in the oxidant is too low, the reaction rate will decrease because the collision chance between oxidant molecules and carbon black particles decreases. If the addition amount of carbon black in the oxidant is too high, the reaction efficiency will decrease due to the aggregation between carbon black particles. Therefore, the addition amount of carbon black in the oxidant needs to be set to 0.1 g / mL - 0.2 g / mL.

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

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

[0039] The present invention will be further described below by way of specific embodiments.

[0040] In the following experimental methods of the embodiments, unless otherwise specified, they are all conventional methods; in the following embodiments, the test materials used, unless otherwise specified, are all obtained by purchasing from commercial channels.

[0041] Example 1

[0042] Carbon black was taken and added to nitric acid. The addition amount of carbon black in nitric acid was 0.1 g / mL, and the reaction was carried out at 70 °C for 10 h, followed by washing and drying to obtain oxidized carbon black;

[0043] After mixing oxidized carbon black, polycarbonate diol and dicyclohexylcarbodiimide in a ratio of 20:1:0.1, the reaction was carried out at 50 °C for 5 h to obtain polycarbonate diol-coated carbon black;

[0044] 20 parts of polycarbonate diol-coated carbon black were taken and added to 15 parts of toluene. 10 parts of toluene diisocyanate and 0.1 part of dibutyltin dilaurate were added, and the reaction was carried out at 80 °C for 20 min. After the reaction, rotary evaporation was carried out;

[0045] 40 parts of hydroxy acrylic resin were taken and added to 15 parts of toluene. The rotary evaporation product was added, and after stirring evenly, it was coated on the substrate and cured to obtain a light-shielding glass film.

[0046] Example 2

[0047] Carbon black was taken and added to hydrogen peroxide. The addition amount of carbon black in hydrogen peroxide was 0.2 g / mL, and the reaction was carried out at 100 °C for 20 h, followed by washing and drying to obtain oxidized carbon black;

[0048] After mixing oxidized carbon black, polycarbonate diol and diisopropylcarbodiimide in a ratio of 20:5:0.5, the reaction was carried out at 80 °C for 10 h to obtain polycarbonate diol-coated carbon black;

[0049] 20 parts of polycarbonate diol-coated carbon black were taken and added to 15 parts of toluene. 10 parts of toluene diisocyanate and 0.1 part of stannous octoate were added, and the reaction was carried out at 100 °C for 40 min. After the reaction, rotary evaporation was carried out;

[0050] 50 parts of hydroxy acrylic resin were taken and added to 30 parts of toluene. The rotary evaporation product was added, and after stirring evenly, it was coated on the substrate and cured to obtain a light-shielding glass film.

[0051] Example 3

[0052] The preparation of polycarbonate diol-coated carbon black is the same as that in Example 1, except that the preparation of the light-shielding layer includes the following steps:

[0053] Take 21 parts of polycarbonate diol-coated carbon black and add it to 15 parts of toluene. Add 15 parts of toluene diisocyanate and 0.5 part of dibutyltin dilaurate, and react at 80 °C for 20 min. After the reaction is completed, perform rotary evaporation;

[0054] Take 41 parts of hydroxy acrylic resin and add it to 20 parts of toluene. Add the rotary evaporation product, stir evenly and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

[0055] Example 4

[0056] The preparation of polycarbonate diol-coated carbon black is the same as that in Example 1, except that the preparation of the light-shielding layer includes the following steps:

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

[0058] Take 42 parts of hydroxy acrylic resin and add it to 25 parts of toluene. Add the rotary evaporation product, stir evenly and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

[0059] Example 5

[0060] The preparation of polycarbonate diol-coated carbon black is the same as that in Example 1, except that the preparation of the light-shielding layer includes the following steps:

[0061] Take 23 parts of polycarbonate diol-coated carbon black and add it to 20 parts of toluene. Add 12 parts of toluene diisocyanate and 0.2 part of dibutyltin dilaurate, and react at 80 °C for 20 min. After the reaction is completed, perform rotary evaporation;

[0062] Take 45 parts of hydroxy acrylic resin and add it to 30 parts of toluene. Add the rotary evaporation product, stir evenly and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

[0063] Example 6

[0064] The preparation of polycarbonate diol-coated carbon black is the same as that in Example 1, except that the preparation of the light-shielding layer includes the following steps:

[0065] Take 24 parts of polycarbonate diol-coated carbon black and add it to 30 parts of toluene. Add 13 parts of toluene diisocyanate and 0.3 part of dibutyltin dilaurate, and react at 80 °C for 20 min. After the reaction is completed, perform rotary evaporation;

[0066] Take 47 parts of hydroxy acrylic resin, add it to 30 parts of toluene, add the rotary evaporation product, stir evenly and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

[0067] Example 7

[0068] The preparation of polycarbonate diol-coated carbon black is the same as that in Example 1, except that the preparation of the light-shielding layer includes the following steps:

[0069] Take 25 parts of polycarbonate diol-coated carbon black, add it to 30 parts of toluene, add 14 parts of toluene diisocyanate and 0.4 part of dibutyltin dilaurate, react at 80 °C for 20 min, and perform rotary evaporation after the reaction ends;

[0070] Take 50 parts of hydroxy acrylic resin, add it to 30 parts of toluene, add the rotary evaporation product, stir evenly and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

[0071] Comparative Example 1

[0072] It is the same as Example 1, except that carbon black is used instead of polycarbonate diol-coated carbon black.

[0073] The light-shielding glass films prepared in Examples 1-7 and Comparative Example 1 were tested, and the test contents are as follows:

[0074] Light-shielding property test:

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

[0076] Table 1

[0077] Visible light transmittance (%) Ultraviolet ray blocking rate (%) Infrared ray 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 all above 60%. At the same time, the ultraviolet blocking rate and infrared blocking rate of Example 1 are greatly improved compared with Comparative Example 1. Therefore, using polycarbonate diol-coated carbon black can improve the light-shielding property of the film.

[0079] Surface hardness test:

[0080] The test was carried out using a pencil hardness tester. The film was smoothly attached to the glass, and pencils with different hardnesses were used to scratch the surface. The hardness of the pencils was gradually increased, and the highest pencil hardness that did not cause 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 has a greater improvement compared to Comparative Example 1. Therefore, using carbonate diol to coat carbon black can improve the surface hardness of the film, thereby enhancing the abrasion resistance of the film and increasing the service life of the film. Moreover, Example 1, Example 3, and Example 4 have higher surface hardness compared to other examples.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been 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 can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the protection scope of the present invention.

Claims

1. A light-shielding glass film, characterized in that Using a polyester film as the 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 hydroxy 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 part of catalyst.

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 hydroxy 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 part of catalyst.

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

4. The preparation method of the light-shielding glass film according to claim 1, characterized in that Comprising: Take polycarbonate diol-coated carbon black and add it to toluene. Add toluene diisocyanate and catalyst, and react at 80°C - 100°C for 20 min - 40 min. After the reaction is completed, perform rotary evaporation. Take hydroxy acrylic resin and add it to toluene. Add the rotary evaporation product, stir evenly, and then coat it on the substrate. After curing, a light-shielding glass film is obtained.

5. The preparation method according to claim 4, characterized in that, The preparation method of the polycarbonate diol-coated carbon black comprises: Take carbon black and add it to an oxidant, react at 70°C - 100°C for 10 h - 20 h, wash, and dry to obtain oxidized carbon black. After mixing oxidized carbon black, polycarbonate diol, and a condensing agent, react at 50°C - 80°C for 5 h - 10 h to obtain polycarbonate diol-coated carbon black.

6. The preparation method according to claim 5, wherein The oxidant is nitric acid or hydrogen peroxide.

7. The preparation method according to claim 5, characterized in that, The addition amount of the carbon black in the oxidant is 0.1 g / mL - 0.2 g / mL.

8. The preparation method according to claim 5, characterized in that, The condensing agent is dicyclohexylcarbodiimide or diisopropylcarbodiimide.

9. The preparation method according to claim 5, characterized in that The mixing ratio of the oxidized carbon black, polycarbonate diol, and condensing agent is 20:(1 - 5):(0.1 - 0.5).