RU2494875C1 - Protective coating for power-saving films - Google Patents

Abstract

FIELD: process engineering.

SUBSTANCE: invention relates to production of translucent power-saving (heat reflection) films with protective coating used for power saving by, for example, gluing them on whatever glazing. Protective coating consists of PEPT film and heat-reflecting spectrum-selective coating applied thereon. Protective coating consists of two layers and comprises adhesive-barrier layer and fluorocarbon polymer layer. Said adhesive-barrier layer comprises polyvinyl butural with UV-absorber (nanosilver). Said fluorocarbon polymer layer comprises copolymer of tri-chlorovinyl with vinyl-butyl ether and monovinyl ether of ethylene glycol, isocyanate hardener, UV-absorber (thynuvin) and polymethyl siloxane. Adhesive-barrier layer is applied on heat-reflecting coating while second fluorocarbon polymer layer is applied thereon.

EFFECT: production of translucent power-saving (heat reflection) films with protective coating used for power saving by, for example, gluing them on whatever glazing.

3 tbl, 13 ex

Description

The invention relates to the field of transparent energy-saving (heat-reflecting) films used for energy saving by gluing them on any type of glazing (windows, stained-glass windows, doors) of buildings and cars.

The simplest energy-saving film consists of a polymer film, usually a polyethylene terephthalate (PET) film coated with a heat-reflecting spectrally selective coating (TSSP).

TSSP can be of two types:

1) Heat reflective spectrally selective inorganic coating, which is applied using magnetron sputtering. In the simplest version, it is a metal layer (gold, silver, copper, nickel, titanium, etc.) with a thickness of about 0.01 μm, enclosed between two layers of dielectrics, usually these are metal oxides, nitrides or oxynitrides (tin, zinc, aluminum, silicon, titanium, niobium, nickel, chromium). The coating structure can be quite complex, the number of layers applied reaches 12 and even more.

2) Polymeric TSSP, consisting of an organic polymer binder and IR and UV absorbing or reflecting components evenly distributed in it - colloidal nanoparticles of metal oxides (nanosized tin, indium, silicon, iron, indium tin, tungstates, etc.), hexaboride lanthanum or organic dyes, which is applied using an irrigation machine from a solution of the polymer composition.

For the manufacture of a self-adhesive energy-saving film, on the opposite side of the PET film from the TSSP, an adhesive layer of constant stickiness is additionally applied and protected by lamination (rolling) with an anti-adhesive film, usually a thin PET film 12-35 μm thick with a silicone coating applied to it. Lamination is carried out with a silicone coating to the adhesive layer of constant stickiness.

Known transparent energy-saving film with a low-emission inorganic TSSP, consisting of a polymer substrate with a multilayer heat-reflecting coating of the type "dielectric-metal-dielectric" applied on one side of it. The film is an optically transparent PET film with a thickness of (35 ± 2) or (50 ± 5) μm, on which TSSP is applied by reactive magnetron sputtering of targets from an aluminum-silicon alloy and silver according to RF patent No. 2132406, consisting of sequentially deposited dielectric layers (aluminum-silicon nitride), metal (silver) and dielectric (aluminum-silicon nitride), and the dielectric is formed in a rarefied atmosphere of a mixture of argon and nitrogen by the reaction of atomized aluminum and silicon atoms with nitrogen molecules to form the corresponding nitrides. In this case, silver atoms do not interact with nitrogen atoms and do not form nitride under these conditions.

The reactions occurring in the vacuum installation can be displayed as follows:

2Al + N ₂ = 2AlN

6Si + 4N ₂ = 2Si ₃ N ₄

The resulting layer of aluminum-silicon nitride AlN-Si ₃ N ₄ resulting from chemical reactions is a dielectric, in contrast to the preceding target material of an aluminum-silicon alloy, which is a metal.

In this case, the preparation of TSSP is carried out in a reaction (under the influence of magnetron radiation) medium at a total pressure of the working mixture of nitrogen and argon no more than 5 · 10 ^-4 mm Hg, where the evaporated silicon and aluminum atoms are transformed in a rarefied atmosphere into particles of silicon nitrides and aluminum, forming further upon deposition on a PET film a dielectric layer of aluminum-silicon nitride. In this case, silver from the target is deposited onto the aluminum-silicon nitride layer preceding it in the form of metallic silver, since silver does not form nitrides under these conditions.

Since the targets are arranged sequentially in the vacuum chamber — the target is made of an aluminum-silicon alloy, the target is made of silver, the target is made of an aluminum-silicon alloy, with a sequential passage of the PET film above them on the surface of the PET film, they consistently form a layer of aluminum-silicon nitride (dielectric) , a silver layer (metal), a layer of aluminum-silicon nitride (dielectric), which provide the heat-reflecting properties of this three-layer coating.

The film is characterized by a high reflection coefficient of thermal radiation, but TSSP has insufficient resistance to both mechanical stresses (when washing glasses, dust exposure) and aggressive media (acidic, alkaline or oxidative effects). Under their influence during operation, the TSSP is destroyed within 1-3 months.

A protective coating is known for metals and polymer composites, consisting of a fluoropolymer, an epoxy diane or fluoroepoxy resin, a hardener-polyisopianate biuret and γ-aminopropyltriethoxysilane. Additionally, the composition may contain a light stabilizer and pigments (RF patent No. 2378307). The specified protective coating is selected as a prototype.

The protective coating of the prototype does not provide reliable protection against the mechanical effects of TSSP energy-saving films, and also does not reduce the transmission of rays in the near UV region of the spectrum, which leads to photo-fading of interior objects (wallpapers, fabrics, paintings, paints, etc.).

An object of the invention is the creation of a protective polymer coating for TSSP energy-saving films, which provides reliable protection of TSSP from mechanical influences and a significant reduction in the transmission of rays in the near UV region of the spectrum, leading to a significant reduction in photo-fading of interior objects (wallpaper, fabrics, paintings, coatings, and etc.).

To solve this problem, we propose a composition for a protective coating, consisting of two layers, the first of which is an adhesive-barrier layer, applied directly to TSSP and consists of polyvinyl butyral (PVB) and a UV absorber - nanosized silver particles (nanosilver), the second layer - a fluoropolymer protective layer, applied on top of the adhesive-barrier layer, and consists of a fluoropolymer, an isocyanate hardener, PMS-300 polymethylsiloxane and a UV absorber (Tinuvin).

Self-adhesive energy-saving film with a protective coating consists of the following successive structural elements: protective coating, TSSP, PET film, adhesive of constant stickiness, release film.

Protective covering Fluoropolymer protective layer Adhesion barrier layer TSSP Aluminum Silicon Nitride Silver Aluminum Silicon Nitride PET film Permanent sticky adhesive Release film Silicone coating PET film Figure 1. Material structure

As a protective coating, a two-layer coating is used, consisting of two layers: an adhesive-barrier and a protective layer.

The adhesive-barrier layer has the following composition:

- PVB - 87.0-95.2;

- nanosilver - 4.8-13.0.

The protective layer has the following composition:

- a copolymer of trifluorochlorovinyl with vinyl butyl ether and monophenyl ether of ethylene glycol FPR-1 - 53.2-75.0;

- Isocyanate hardener JarLI No. 31 - 11.9-33.8;

- Tinuvin P - 13.0-23.1;

- polymethylsiloxane - 0.08-0.81,

moreover, the adhesive-barrier layer is applied to the TSSP energy-saving film, and the protective layer is applied to the adhesive-barrier layer.

As TSSP, for example, a coating consisting of the following three layers of the following composition can be used:

- A layer of aluminum-silicon nitride alloy,

- A layer of silver

- A layer of aluminum-silicon nitride alloy,

obtained by vacuum spraying targets from an aluminum-silicon alloy and from silver in a rarefied atmosphere of argon-nitrogen.

Coatings obtained by the method of irrigation using a solution of a polymer composition using an irrigation machine and including an organic polymer binder and IR and UV absorbing or reflecting components uniformly distributed in it — colloidal nanoparticles of metal oxides (nanosized tin, indium, silicon) can also be used as TSSP , iron, indium tin, tungstates, etc.), lanthanum hexaboride or organic dyes.

As a layer of glue of constant stickiness, acrylate glue of constant stickiness can be used.

As a release film, a PET film with a silicone release coating applied to it can be used.

A protective coating for energy-saving films consisting of PET film and TSSP is obtained by applying an adhesive-barrier layer composition to TSSP and then applying a fluoropolymer protective layer composition to the adhesive-barrier layer. The protective coating after drying has the following composition, wt.%:

1) the composition of the adhesive-barrier layer:

- PVB - 87.0-95.2,

- UV absorber (nanosilver) - 4.8-13.0;

2) the composition of the fluoropolymer protective layer:

- fluoropolymer (a copolymer of trifluorochlorovinyl with vinyl butyl ether and ethylene glycol monovinyl ether) - 53.2-75.0,

- isocyanate hardener (di-, tri or polyisocyanate) - 11.9-33.8,

- UV absorber (tinuvin) - 13.0-23.1,

- polymethylsiloxane - 0.08-0.81.

As an organic solvent, the composition of the adhesive-barrier layer contains isopropyl alcohol, the composition of the fluoropolymer protective layer is solvent P-4.

For the manufacture of a self-adhesive energy-saving film, an acrylate adhesive layer of constant stickiness is additionally applied to the side of the PET film on the opposite side from the TSSP and the adhesive layer is protected by lamination (rolling) with an anti-adhesive film, which is a thin PET film 12-25 μm thick with a silicone coating applied to it. Lamination is carried out with a silicone coating to the adhesive layer of constant stickiness.

This goal is achieved by the use of polymethylsiloxane in the fluoropolymer protective layer, which provides high mechanical resistance to abrasion, as well as the combined use of nalosilver in the protective coating, which absorbs in the far and near UV regions of the spectrum and tinuvin, which absorbs in the middle UV region of the spectrum.

Polyvinyl butyral used in the adhesive-barrier layer does not affect the thermophysical characteristics of TSSP and provides high adhesion of the adhesive-barrier layer of the protective coating to TSSP.

The cured fluoropolymer in combination with polysiloxane forms a protective layer on the surface of the adhesive-barrier layer, characterized by high mechanical strength and resistance to aggressive environments.

To achieve a technical result in the present invention, silver nanopowders of the AGP-P025 brand (manufacturer Huzheng Nano, Ltd., Shanghai, China) and Tinuvins: Tinuvin P (Benazol P), Tinuvin 1130, Tinuvin 292 were used as UV absorbers.

As a fluoropolymer, a copolymer of trifluorovinyl vinyl with vinyl butyl ether and ethylene glycol monovinyl ether with a hydroxyl content of 1.3-2.5% was used. The main representatives of such polymers are, for example, FPR-1 and FPR-2 according to TU 2313-052-00203521-99 with a mass fraction of non-volatile substances 30-40 wt.%. Di-, tri- and polyisocyanates are used as a hardener, for example, YarLi hardeners according to TU 2332-217-21743165-2001.

Examples of specific performance.

Example 1 (prototype)

0.93 kg (40% solution) of FPR-1 fluorine-containing varnish with a hydroxyl content of 2.2% was weighed in a special container. Then, 0.04 kg of γ-aminopropyltriethoxysilane in a mixture of 0.24 kg of xylene, 0.18 kg of ethyl cellosolve and 0.08 kg of methoxypropyl acetate of organic solvents were introduced into 0.07 kg of epoxy diane resin E-40. The composition was mixed with 0.93 kg of fluorinated varnish ФПР-1, mixed until a uniform solution was formed. Then, 0.15 kg of polyisocyanate biuret and 0.15 kg of Tinuvin P were introduced into the solution, and then mixed again to obtain the finished composition.

The resulting composition was applied by the method of a bathing roller on an MP-300 irrigation machine with a PET film speed of 1 m / min and a tape length of 12 m on a PET film with a low-emission transparent inorganic TSSP deposited, as described in Example 2; the applied layer of the protective coating composition was dried in the path of the irrigation machine. The drying temperature of the protective composition gradually increases from room temperature (after the application unit) to 80 ° C (in front of the winding unit). The resulting thickness of the protective coating is 8 ± 2 μm with the content of dry components, wt.%:

- Fluoropolymer FPR-1 - 47.57 - Epoxy Dianova Resin - 8.95 - γ-aminopropyltriethoxysilane - 5.12 - Polyisocyanatobiuret - 19.18 - Tinuvin P - 19.18

Example 2

a) Application of a low-emission transparent inorganic TSSP to a PET film.

The low-emission transparent inorganic TSSP by the method of magnetron sputtering of targets is applied to a PET film in three layers in the following order: dielectric (aluminum-silicon nitride), metal (silver), dielectric (aluminum-silicon nitride), and the dielectric layers are obtained in a rarefied atmosphere with an argon mixture with nitrogen. A three-layer coating is applied to a vacuum-spraying machine designed for coating roll materials. The PET film, rolled up, is loaded into the vacuum chamber of the installation, where during the production cycle it passes through several working compartments using a rewind system. In the working compartments at a distance of 80 mm from the PET film, magnetron sputtering sources are installed with 1 silver target and 6 targets of the eutectic alloy of aluminum and silicon (Al-Si) alloy. Argon and nitrogen are fed into the working compartments of magnetrons with targets from an aluminum-silicon alloy; the total pressure of the mixture does not exceed 5 · 10 ^-4 mm Hg. Art. The spraying of metals is carried out at a discharge current density of 25 mA / cm ² .

The substrate sequentially passes at a speed of 3 m / min past magnetrons with targets from an aluminum-silicon alloy, then with a target from silver and again with targets from an aluminum-silicon alloy. As a result, a layer of aluminum-silicon nitride (30 ± 20 nm), silver (15 ± 5 nm), a layer of aluminum-silicon nitride (30 ± 20 nm) are sequentially deposited on a PET film.

b) Preparation of the composition of the adhesive-barrier layer.

475 g of isopropyl alcohol is poured into a special container, and then 25 g of varnish PVB are added with vigorous stirring. The resulting mixture was stirred at room temperature until the PVB was completely dissolved. After that, 1.26 g of silver nanopowder is added to the resulting solution, stirred for one hour and filtered through a nylon mesh with a cell diameter of 20 μm, obtaining a composition of the adhesive-barrier layer.

c) Preparation of a composition of a fluoropolymer protective layer.

330 g of FPR-1 copolymer are loaded into a special container and diluted with solvent R-4 with stirring to a viscosity of 15-20 s using a B3-4 viscometer. Then, to the resulting solution, 22.95 g of Tinuvin P (Benazol P) and 21 g of Hardener No. 31 hardener are added with stirring. The resulting composition was stirred for 30 minutes and filtered through a nylon mesh with a cell diameter of 20 μm, obtaining a composition of a fluoropolymer protective layer.

d) Application and drying of the adhesive-barrier and fluoropolymer protective layers on a low-emission transparent inorganic TSSP.

The prepared adhesive-barrier composition is applied to a PET film with a low-emission transparent inorganic TSSP on a TSSP layer by the bathing roller method on an MP-300 irrigation machine at a speed of movement of a PET film of 1 m / min, a width of a PET film of 300 mm and a tape length of 12 m, applied the layer is dried. The drying temperature of the applied composition gradually increases from room temperature (after the application unit) to 80 ° C (in front of the winding unit). The resulting thickness of the adhesive-barrier layer is 4 ± 1 μm. A composition of a fluoropolymer protective layer is applied to a PET film coated with TSSP and an adhesive-barrier layer by the method of a bathing roller on an MP-300 irrigation machine at a speed of movement of a PET film of 1 m / min, a width of a PET film of 300 mm and a tape length of 12 m, the applied layer are dried. The resulting thickness of the fluoropolymer protective layer is 4 ± 1 μm.

Examples 3-13

Samples of energy-saving films with protective layers of various compositions are made as in example 2.

The compositions of the dry adhesive-barrier layer and the fluoropolymer protective layer are shown in table 1.

Table 1 Example No. Adhesion-barrier layer, wt.% Fluoropolymer protective layer, wt.% PVB Nanosilver FPR-1 Hardener Tinuvin P PMS-300 2 95.2 4.8 75.0 11.9 13.1 - 3 95.2 4.8 53,2 33.8 13.0 - four 95.2 4.8 66.0 21.0 13.0 - 5 87.0 13.0 66.0 21.0 13.0 - 6 90.9 9.1 66.0 21.0 13.0 - 7 90.9 9.1 58.3 18.6 23.1 - 8 90.9 9.1 61.9 19.7 18,4 - 9 90.9 9.1 61.9 19.7 18.4 *) - 10 90.9 9.1 61.9 19.7 18.4 **) - eleven 90.9 9.1 61.86 19.69 18.37 0.08 12 90.9 9.1 61.41 19.54 18.24 0.81 13 90.9 9.1 61.64 19.61 18.30 0.45 *) Tinuvin 1130; **) Tinuvin 292.

To obtain self-adhesive energy-saving films with a protective layer, on the opposite side of the TSSP, the PET films are applied with an adhesive composition based on acrylate adhesives of constant stickiness (for example: Acrylate 85 CT, Alfa-103, Lacrylene-1003, AKPL glue, Acrylate K-5 "). The dried adhesive layer is laminated with a PET film 35 ± 2 μm thick containing silicone release coating. The thickness of the adhesive layer is 15-20 microns.

The resulting protective coating is determined by hardness by testing with a pencil according to ISO 15184. Varnishes and paints. Hardness test with a pencil test.

The essence of the method is to draw a coating with a pencil of a certain hardness (KOH-I-NOOR pencils of the following hardness: 9V-8V-7V-6V-5V-4V-3B-2B-B-HB-FH-2H-3H-4H-5H- 6H-7H-8H-9H) at an angle of 45 ° and a load of 750 g using an automatic testing device with subsequent evaluation of the test results. For testing, sharpen a pencil by removing only the tree and leaving the lead cylindrical. The pencil is inserted into the test device so that it touches the coating. Then draw a pencil on the coating line with a length of at least 7 mm at a speed of 0.5 mm / s to 0.1 mm / s. After 30 s, a trace of the pencil is removed with soft cotton and the test results are evaluated visually or using a magnification of 6-10 ^x . If the coating is not visually broken, test with a pencil of greater hardness to obtain the effect.

The data obtained are shown in table 2.

table 2 Example No. Prototype 2 3 four 5 6 7 8 9 10 eleven 12 13 Hardness 3H 7H 6H 6H 6H 6H 6H 6H 6H 6H 7H 7H 8H

Next, the ability of films with a protective layer to reduce UV radiation, i.e. protective ability of samples.

Using a Canon Pixma iP 4800 inkjet printer using water-based dye inks and matte inkjet paper, 15 × 15 mm red squares were recorded from magenta and yellow inks (the least lightfast). Then, film samples with protective coatings were applied to these squares. Samples from the protective film side were exposed to UV radiation in a Proxima copy frame (LUF-80 fluorescent lamps with a total power of 800 W) for 96 hours. The color coordinates of the samples before and after exposure were determined using an X-Rite Digital Swatchbook spectrophotometer, and the ΔЕ value corresponding to the color change (fading) of red squares was used to judge the light-shielding ability of a film with a protective layer, and lower values of ΔЕ correspond to a higher light-shielding ability (lower UV transmission).

The data obtained are shown in table 3.

Table 3 Example No. Prototype 2 3 four 5 6 7 8 9 10 eleven 12 13 Fading ΔE 18.6 10,2 11.0 10.8 8.0 8.9 8.0 8.5 8.3 8.5 8.7 8.6 8.6

For all samples, including the prototype, tests were carried out for resistance to aggressive environments (acid, alkaline, oxidative and reducing effects). All samples were immersed for 48 hours in desiccators with aggressive agents: acid (1% aqueous solution of hydrochloric acid HCl), alkali (2% aqueous solution of ammonia NH ₃ ), oxidizing agent (1.5% aqueous solution of sodium hypochlorite NaClO) and a reducing agent (1% aqueous solution of Na ₂ S).

The visual and spectral characteristics of the test samples, including the prototype, did not change as a result of tests for resistance to aggressive environments.

As follows from a comparative analysis of the test data of the prototype and examples of specific performance presented in tables 2, 3, the proposed protective coating can significantly increase the mechanical strength of the coating and increase the resistance of objects to photo-fading by reducing the transmission of near UV radiation without compromising resistance to aggressive environments .

INFORMATION SOURCES

1. RF patent No. 2132406, IPC С23С 14/06, 1999

2. RF patent No. 2378307, IPC С09D 127/12, 2010

Claims (1)

A protective coating for energy-saving films consisting of a polyethylene terephthalate film and a heat-reflecting spectrally selective coating, including an adhesive-barrier layer of the following composition:
polyvinyl butyral 87.0-95.2
nanosilver 4.8-13.0
and a fluoropolymer protective layer of the following composition:
copolymer of trifluorochlorovinyl with vinyl butyl ether and mono-vinyl ether of ethylene glycol FPR-1 53.2-75.0
Isocyanate hardener JarLI No. 31 11.9-33.8
Tinuvin P 13.0-23.1
polymethylsiloxane 0.08-0.81
moreover, the adhesive-barrier layer is deposited on a heat-reflecting spectrally selective coating, and the fluoropolymer protective layer is deposited on the adhesive-barrier layer.