RU2432263C1 - Wallpapers with air cleaning functions and method of their production - Google Patents

Abstract

FIELD: process engineering. ^ SUBSTANCE: invention relates to residential ecology, particularly, to wallpapers with air cleaning properties and method of their production. Wallpaper comprises substrate, printed layer and air cleaning cover layer arranged in said order starting from bottom. Air cleaning cover layer is formed by applying photo catalyst layer to be activated by visible band light. Photo catalyst comprises solvent, titanium compound, gelating agent, metal compounds and acid catalyst. Besides, invention covers the method of producing above described wallpapers. ^ EFFECT: air cleaning wallpapers activated by whatever room illuminators. ^ 14 cl, 3 dwg, 6 tbl, 2 ex

Description

State of the art

1. The technical field to which the invention relates.

The present invention relates to air cleaning wallpapers and a method for manufacturing such air cleaning wallpapers. More specifically, the present invention relates to air cleaning wallpapers, which can have satisfactory photocatalytic activity under the influence of low-power (low-energy) light sources, such as incandescent and fluorescent lamps, and also under the action of high-energy light sources, such as UV radiation and sunlight , and to a method of manufacturing an air cleaning wallpaper.

2. Description of the Related Art

There are many ways to give wallpaper deodorizing functions. For example, a porous adsorbent is applied to the wallpaper. In order for the desired effects to manifest, a porous adsorbent is located on the surface of the wallpaper. In order to attach the adsorbent to the wallpaper, a coating solution is applied to the wallpaper containing an adsorbent to form a coating layer on the surface. However, in this case, the glue clogs the pores of the adsorbent, making it difficult for the adsorbent to perform the deodorizing function. Typically, the adsorbent is a particle of about several tens of microns in size and has a black color. The adsorbent coating on the surface of the wallpaper impairs the printability of the wallpaper.

When trying to create a clean indoor environment, methods were proposed in which the photocatalyst photoactivity is used to remove indoor air pollutants. In this regard, the use of photocatalysts, a typical representative of which is titanium dioxide, is being actively studied.

Titanium dioxide based photocatalysts have attracted much attention and interest as environmentally friendly materials that convert light energy into chemical energy at room temperature. In recent years, titanium dioxide-based photocatalysts have been widely used in various fields, including indoor air cleaning, in antibacterial and deodorizing materials. Significant research achievements have also been made in the field of increasing the photoactivity of titanium dioxide-based photocatalysts. In particular, one of the approaches to increasing the photoactivity of titanium dioxide is considered to reduce the particle size of titanium dioxide to the nanometer range and the addition of metal to titanium dioxide, such as platinum, silver or nickel.

Well-known photocatalytic coatings are sensitive to UV radiation, however, their effects are not expected to be exposed to visible light in a normal environment. Photocatalyst particles can interact in a coating solution, which must be applied to form a surface layer. Such interaction can cause aging of the surface layer. In addition, UV-sensitive photocatalysts are activated even under the influence of UV radiation or sunlight, which limits their use and serves as an obstacle to expand their range and applications.

SUMMARY OF THE INVENTION

The authors of the present invention analyzed the effect of various metals on the photocatalytic effects of titanium dioxide doped with metal ions. As a result, the authors of the present invention found that a photocatalyst doped with ions of certain metals effectively absorbs light not only in the UV range, but also in the visible wavelength range (about 400-800 nm) of light from incandescent lamps, fluorescent lamps, and LED (LED) ) lamps, etc., which was previously considered an intractable problem, and has good activity. Based on this discovery, the authors of the present invention used a doped photocatalyst for wallpaper coatings.

Thus, it is an object of the present invention to provide air-cleaning wallpapers that have an air-cleaning surface coating formed on the wallpapers by spray coating to deodorize the air and remove formaldehyde and unpleasant odors released during daily life, while maintaining their deodorizing effect even under the influence of low-energy light in the visible wavelength range from indoor incandescent lamps, fluorescent lamps, light iodine (LED) lamps, etc., and insufficient light intensity; a coating that does not cause wallpaper aging and does not damage the appearance of the wallpaper.

According to one aspect of the present invention, there is provided an air cleaning wallpaper comprising a base layer, a printed layer and an air cleaning coating layer formed in the order shown below, where the air cleaning coating layer is formed by coating with a photocatalyst that is activated by visible light and contains a solvent, a titanium compound , chelating agent, metal compounds and acid catalyst.

The photocatalyst activated by visible light may further comprise a binder.

The binder may be triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane, or a mixture thereof.

The solvent may be a C ₁ -C ₄ alcohol.

The alcohol may be isopropanol.

The titanium compound may be titanium tetraisopropylate.

The chelating agent may be ethylenediaminetetraacetic acid (EDTA) or diacetylmethane.

Metal compounds can be selected from the group consisting of nitrates, sulfates and chlorides of zinc, copper, iron, manganese, lithium and silver.

The acid catalyst may be hydrochloric acid, nitric acid, sulfuric acid, or acetic acid.

According to another aspect of the present invention, there is provided a method for manufacturing air-cleaning wallpapers, comprising: (a) reacting an alcohol, a titanium compound and a chelating agent; (b) dissolving metal compounds in distilled water; (c) adding the reaction mixture from step (a) to the aqueous solution from step (b) in the presence of an acid catalyst and reacting the resulting mixture with stirring to obtain a photocatalyst activated by visible light; and (d) coating the wallpaper with a photocatalyst activated by visible light.

The method of the present invention may further include adding a binder after the reaction in step (c).

According to an embodiment of the present invention, there is provided a method for manufacturing an air-cleaning wallpaper comprising: (a) reacting isopropanol as an alcohol, titanium tetraisopropylate as a compound of titanium and diacetylmethane as a chelating agent; (b) dissolving nitrates of two, three or four metals selected from nitrates of Zn, Cu, Fe, Mn, Li and Ag as metal compounds in distilled water; (c) slowly adding the reaction mixture from step (a) to the aqueous solution from step (b) in a temperature range from room temperature to 90 ° C., and reacting the resulting mixture with stirring at 90 rpm or higher for at least , 2 hours in the presence of nitric acid as an acid catalyst; (d) adding to the reaction mixture from step (c) triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane or a combination thereof as a binder to obtain a photocatalyst activated by visible light; and (e) coating the wallpaper with a photocatalyst coating activated by visible light.

Coating can be carried out by spray coating.

Brief Description of the Drawings

These and / or other aspects and advantages of the invention will become apparent and will be more readily appreciated from the following description of embodiments of the invention, given together with the accompanying drawings, in which:

figure 1-3 shows experimental data showing the rate of removal of formaldehyde using wallpaper in example for comparison 1 and wallpaper in example 1.

DETAILED DESCRIPTION OF THE INVENTION

Here will be described in detail typical embodiments of the present invention.

The present invention provides an air-cleaning wallpaper comprising a base layer, a printed layer and an air-cleaning coating layer formed in this order starting from the bottom, where the air-cleaning coating layer is formed by coating from a photocatalyst that is activated by visible light and contains a solvent, a titanium compound, a chelating agent agent, metal compounds and acid catalyst.

The present invention also provides a method for manufacturing an air cleaning wallpaper, comprising: (a) reacting an alcohol, a titanium compound and a chelating agent; (b) dissolving metal compounds in distilled water; (c) adding the reaction mixture from step (a) to the aqueous solution from step (b) in the presence of an acid catalyst, and reacting the resulting mixture with stirring to obtain a photocatalyst activated by visible light; and (d) coating the wallpaper with a photocatalyst activated by visible light.

The individual steps of the method of the present invention will be described below.

Stage (a)

Alcohol, a titanium compound and a chelating agent can be added in any order. The reaction is carried out with sufficient stirring until the evolution of heat ceases, since the reaction is highly exothermic. The titanium compound may be any of the titanium compounds known in the art. The use of titanium tetraisopropylate (TTIP) as an organic titanium compound is preferable in terms of stable delivery and ease of handling.

The alcohol may be a lower C ₁ -C ₄ alcohol. A typical example of a lower C ₁ -C ₄ alcohol is isopropanol. Alcohol is used in an amount of 0.5 to 5.00 mol per mol of titanium tetraisopropylate. Outside the specified range, the functional characteristics of the final catalyst are unsatisfactory.

A chelating agent is used so that the titanium compound interacts uniformly and stably. Examples of chelating agents suitable for use in the present invention include ethylenediaminetetraacetic acid (EDTA) and diacetylmethane. The use of diacetylmethane is preferred in terms of reactivity. A chelating agent can be added in an amount of from 0.1 to 1.00 mol per mol of titanium compound. Outside the specified range, satisfactory functional characteristics of the final catalyst cannot be expected.

Stage (b)

At this stage, distilled water is used in an amount of 25 to 550 mol per mol of titanium compound.

As metal compounds, salts of two, three or four metals selected from salts of Zn, Cu, Fe, Mn, Li and Ag can be used. Metal salts may be nitrates, sulfates or chlorides.

Stage (s)

At this stage, the reaction mixture from stage (a) is slowly added to the aqueous solution from stage (b) in the temperature range from room temperature to 90 ° C, and then the resulting mixture is reacted with stirring at 90 rpm or higher for at least at least 2 hours in the presence of an acid catalyst to obtain a photocatalyst activated by visible light.

As the acid catalyst, for example, hydrochloric acid (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ) or acetic acid (CH ₃ COOH) can be used. Nitric acid or hydrochloric acid is preferred. In the Examples section of the present invention, nitric acid was used in an amount of from 0.10 to 0.50 mol per mol of titanium compound. Outside the specified range, satisfactory functional characteristics of the final catalyst are not observed.

Stage (d)

At this stage, air-cleaning wallpapers are made by applying a photocatalyst activated by visible light on the surface of the wallpaper. The coating can be carried out by any suitable coating method known in the art. Spray coating is preferred. According to the prototype, in a method for manufacturing a photocatalyst coated wallpaper, the photocatalyst particles present in the coating solution cause the surface of the base wallpaper to age. In contrast, according to the method of the present invention, a coating layer formed on the outer surface of the base wallpaper by spray coating protects the base wallpaper from damage to the appearance (for example, from aging).

Stage (e)

This stage is optional, and not necessary. A binder can be added after any of steps (a), (b) and (c). Most preferably, step (e) is carried out after step (c). The binder may be triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane, or a combination thereof. It is desirable to add a binder in an amount of from 0.001 to 0.20 mol per mol of titanium compound. The duration of the reaction is limited to a maximum of 120 minutes after adding the binder.

In a specific embodiment of the present invention, the method may include: (a) reacting isopropanol as an alcohol, titanium tetraisopropylate as a compound of titanium and diacetylmethane as a chelating agent; (b) dissolving nitrates of two, three or four metals selected from nitrates of Zn, Cu, Fe, Mn, Li and Ag as metal compounds in distilled water; (c) slowly adding the reaction mixture from step (a) to the aqueous solution from step (b) in a temperature range from room temperature to 90 ° C., and reacting the resulting mixture with stirring at 90 rpm or higher for at least , 2 hours in the presence of nitric acid as an acid catalyst; (d) adding to the reaction mixture from step (c) triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane or a combination thereof as a binder to obtain a photocatalyst activated by visible light; and (e) coating the wallpaper with a photocatalyst coating activated by visible light.

Below, the present invention will be explained in more detail with reference to the following examples. However, the examples mentioned are given for illustrative purposes only and are not intended to limit the scope of the invention.

EXAMPLES

Example 1

142 g of titanium tetraisopropylate, 72 g of isopropanol and 10 g of diacetylmethane are reacted in the first reactor at room temperature for 30 minutes. In a second reactor, 1.4 g of ferric nitrate, 2.6 g of zinc nitrate and 1.8 g of copper nitrate are completely dissolved in 760 g of distilled water with stirring at 400 rpm. Then the reaction mixture from the first reactor is slowly added to the aqueous solution from the second reactor, in addition, 1.6 g of nitric acid are added dropwise. The resulting mixture was heated to 80 ° C and allowed to interact for 3 hours. The reaction mixture was reacted with 7.6 g of triethylorthosilicate for 1 hour. As a result of the reaction, a transparent photocatalyst is obtained — titanium dioxide activated by visible light.

The photocatalyst is applied to the surface of the wallpaper in an amount of 1-20 g / m ² by spraying.

Example for comparison 1

Applied wallpaper without photocatalyst coating.

Experimental Example 1

The formaldehyde removal rates of the wallpaper obtained in Comparative Example 1 and Example 1 were measured according to the following procedure. After each test, pieces of wallpaper were placed in a tedlar bag (polyvinyl fluoride bag), 80 ppm formaldehyde was introduced into the tedlar bag, followed by sealing. The amount of formaldehyde remaining in the tedlar bag after exposure to a fluorescent lamp was measured every 30 min for 120 min (first experiment). Then the procedure of the first experiment was repeated (second experiment). After the second experiment, the procedure of the first experiment was repeated, except that the test piece was placed in a tedlar packet saturated with formaldehyde (third experiment). The results are shown in table 1 (example for comparison 1) and table 2 (example 1) and are shown graphically in figure 1.

Table 1 0 min 30 minutes 60 min 90 min 120 min First experiment 80 47.3 41.6 38.7 36,2 Second experiment 80 50,2 46.3 43.1 40.9 Third experiment Oversaturated 61.7 58.8 57.3 56.7

table 2 0 min 30 minutes 60 min 90 min 120 min First experiment 80 25.6 20.5 15.1 12 Second experiment 80 26 18.8 14,4 11.2 Third experiment Oversaturated 35.6 29.3 27 22.8

The results shown in tables 1 and 2 show that the wallpaper in example 1 had a higher rate of removal of formaldehyde than the wallpaper in example for comparison 1. In addition, the rates of removal of formaldehyde by the wallpaper in example 1 were kept constant even when the number experiments increased.

Experimental Example 2

The procedure of Experimental Example 1 was repeated except that 70 ppm of formaldehyde was introduced in the first and second experiments. The results are shown in table 3 (example for comparison 1) and table 4 (example 1) and are shown graphically in figure 2.

Table 3 0 min 30 minutes 60 min 90 min 120 min First experiment 70 46.8 35.1 27.3 25.5 Second experiment 70 63,4 59 55.1 53.6 Third experiment Oversaturated 50.6 40.9 35.1 33.8

Table 4 0 min 30 minutes 60 min 90 min 120 min First experiment 70 23,4 16,2 9.1 8.5 Second experiment 70 26 18.5 10,4 7.8 Third experiment Oversaturated 33 27.6 22.2 twenty

Experimental Example 3

The procedure of Experimental Example 1 was repeated except that 100 ppm of formaldehyde was introduced in the first and second experiments. The results are shown in table 5 (example for comparison 1) and table 6 (example 1) and are shown graphically in figure 3.

Table 5 0 min 30 minutes 60 min 90 min 120 min First experiment one hundred 48 40 36 33 Second experiment one hundred 58 53.3 49.7 47.4 Third experiment Oversaturated 68.9 65 63 62,4

Table 6 0 min 30 minutes 60 min 90 min 120 min First experiment one hundred eighteen 10 8 6 Second experiment one hundred 21.5 16,2 13 10.6 Third experiment Oversaturated fifty 40.7 36 32

As is evident from the foregoing, the air purifying wallpaper of the present invention continuously exhibits satisfactory photocatalytic activity even under the influence of low-power (low-energy) light sources such as incandescent lamps, fluorescent lamps and LED lamps. Therefore, the air purifying wallpaper of the present invention can be applied in various places, including places where satisfactory effects cannot be achieved with conventional photocatalyst coated wallpapers. In addition, the air cleaning wallpaper of the present invention can be used for a long period of time without affecting the appearance of the base wallpaper.

Claims (14)

1. An air-cleaning wallpaper comprising a base layer, a printed layer and an air-cleaning coating layer formed in the indicated order starting from the bottom, where the air-cleaning coating layer is formed by coating from a photocatalyst that is activated by visible light and contains a solvent, a titanium compound, a chelating agent, metal compounds and acid catalyst. 2. The air purifying wallpaper according to claim 1, wherein the photocatalyst activated by visible light further comprises a binder. 3. Air purifying wallpaper according to claim 2, in which the binder is a triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane or a mixture thereof. 4. Air purifying wallpaper according to claim 1, in which the solvent is a C ₁ -C ₄ alcohol. 5. Air purifying wallpaper according to claim 4, in which the alcohol is isopropanol. 6. The air purifying wallpaper of claim 1, wherein the titanium compound is titanium tetraisopropylate. 7. The air purifying wallpaper according to claim 1, wherein the chelating agent is ethylenediaminetetraacetic acid (EDTA) or diacetylmethane. 8. The air purifying wallpaper according to claim 1, wherein the metal compounds are selected from the group consisting of nitrates, sulfates and chlorides of zinc, copper, iron, manganese, lithium and silver. 9. The air purifying wallpaper according to claim 1, wherein the acid catalyst is hydrochloric acid, nitric acid, sulfuric acid or acetic acid. 10. A method of manufacturing an air cleaning wallpaper, including:
(a) the interaction of an alcohol, a titanium compound and a chelating agent;
(b) dissolving metal compounds in distilled water;
(c) adding the reaction mixture from step (a) to the aqueous solution from step (b) in the presence of an acid catalyst and reacting the resulting mixture with stirring to obtain a photocatalyst activated by visible light; and
(d) coating the wallpaper with a photocatalyst activated by visible light. 11. The method of claim 10, further comprising adding a binder after the interaction in step (c). 12. A method of manufacturing an air cleaning wallpaper, including:
(a) reacting isopropanol as an alcohol, titanium tetraisopropylate as a compound of titanium and diacetylmethane as a chelating agent;
(b) dissolving nitrates of two, three or four metals selected from nitrates of Zn, Cu, Fe, Mn, Li and Ag as metal compounds in distilled water;
(c) slowly adding the reaction mixture from step (a) to the aqueous solution from step (b) in a temperature range from room temperature to 90 ° C. and reacting the resulting mixture with stirring at 90 rpm or higher for at least 2 hours in the presence of nitric acid as an acid catalyst;
(d) adding to the reaction mixture from step (c) triethylorthosilicate, γ-glycidoxypropyltrimethoxysilane or a combination thereof as a binder to obtain a photocatalyst activated by visible light; and
(e) applying a photocatalyst coating activated by visible light to the wallpaper. 13. The method according to claim 10 or 11, in which the coating is applied by spraying. 14. The method according to item 12, in which the coating is applied by spraying.

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