JP3477164B2 - Method for producing titanium oxide-attached base material and curtain fabric - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a titanium oxide-adhered substrate and a curtain material, and more specifically, to a titanium oxide having a uniform thickness and a strong strength, regardless of the heat resistance of the substrate. The present invention relates to a titanium oxide-attached base material and a curtain cloth manufacturing method, which can be formed into a thin film and has excellent decomposition performance for harmful gases and the like. INDUSTRIAL APPLICABILITY The present invention is used for manufacturing interior fabrics such as curtains, upholstery and wallpaper, clothing fabrics and industrial materials.

[0002]

2. Description of the Related Art Conventionally, a photocatalytic function such as titanium oxide has been used for the purpose of decomposing harmful substances. Most of them are formed by forming titanium oxide or the like on the surface of a substrate by a sol-gel method, a vacuum deposition method, a sputtering method, a CVD method or the like. However, when titanium oxide or the like is formed by these methods, most of the titanium oxide or the like is buried in the binder, or the adhesion is not sufficient and the titanium oxide or the like peels off or falls off due to some friction. The current situation is that a sufficient photocatalytic function is not obtained.

Further, in many of these methods, heat treatment at a high temperature is required, and it is difficult to deposit titanium oxide or the like on a substrate having poor heat resistance. Furthermore,
A thin film of titanium oxide or the like can be formed with a uniform thickness on a substrate with a flat surface, but it is difficult to form a thin film with a three-dimensional structure such as a fiber material. Met.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, regardless of the heat resistance of the substrate,
Titanium oxide can be firmly formed on a base material with a uniform thickness, and harmful substances such as nitrogen oxides, sulfur oxides, aldehydes,
Air (gas) containing harmful substances such as pathogenic bacteria and molds]
It is an object of the present invention to provide a titanium oxide-adhered base material and a method for producing a curtain fabric, which have excellent decomposition performance in the decomposition.

[0005]

A method for producing a titanium oxide-adhered substrate according to claim 1 is to immerse the substrate in an aqueous solution containing a fluorotitanium complex compound, an alkali agent and an organic acid, or to prepare the aqueous solution. It is characterized in that it is applied to the base material to deposit titanium oxide on the surface of the base material.

The above-mentioned "fluorotitanium complex compound" includes potassium titanium fluoride, sodium titanium fluoride,
Examples thereof include lithium titanium fluoride, rubidium titanium fluoride, cesium titanium fluoride, and ammonium titanium fluoride. Of these, potassium titanium fluoride and ammonium titanium fluoride are preferably used. The content of this fluorotitanium complex compound is 0.1 to 30 g / L (especially 1 to 8 g / L, more preferably 2 to 4) in the above aqueous solution.
g / L) is preferable. This content is 0.1g
If it is less than / L, titanium oxide may not be sufficiently precipitated. On the other hand, if it exceeds 30 g / L, it may not be sufficiently dissolved.

Examples of the above-mentioned "alkaline agent" include sodium hydrogen carbonate, anhydrous sodium carbonate, sodium hydroxide, potassium hydroxide, dibasic sodium phosphate and tribasic sodium phosphate. Of these, sodium hydrogen carbonate is preferred. The content of the alkaline agent is 0.01 to 5 g / L (especially 0.1 to 1 g / L) in the aqueous solution.
L, more preferably 0.2 to 0.5 g / L). If this content is less than 0.01 g / L, titanium oxide may not be sufficiently precipitated. On the other hand, this is 5
If it exceeds g / L, the precipitation rate of titanium oxide particles may become too fast, secondary aggregation of particles may occur, and the size of the particles to be adhered may not be uniform.

Examples of the above-mentioned "organic acid" include acetic acid, formic acid, citric acid and malic acid. These may be used alone or in combination of two or more.
Among them, as shown in claim 3, (1) malic acid alone,
Alternatively, (2) malic acid and citric acid are preferably used in combination. The content of this organic acid is 0.001 to 1 g / L (especially 0.005 to 0.1 g) in the above aqueous solution.
/ L, and more preferably 0.01 to 0.05 g / L). When this content is less than 0.001 g / L, secondary aggregation of titanium oxide particles may be caused. On the other hand, if it exceeds 1 g / L, the titanium oxide particles may not be sufficiently precipitated.

Further, as described in claim 4, the content of the fluorotitanium complex compound in the aqueous solution is 0.1 to 30 g / L, and the content of sodium hydrogencarbonate as the alkaline agent is 0.01. ˜5 g / L, and the content of the organic acid can be 0.001 to 1 g / L.

The "base material" is not particularly limited, but examples thereof include fiber materials such as woven and non-woven fabrics, plastic materials, inorganic materials such as metals and ceramics, and the like. Further, as described in claim 5, the base material is preferably a woven cloth. Examples of the woven fabric include those made of fibers such as wool, cotton, hemp, silk, rayon, acetate, acrylic and polyester. Furthermore, this woven fabric is claim 6.
It may consist of wool fibers or polyester fibers, as shown in.

The titanium oxide formed on the surface of the substrate has a thickness of 0.001 to 0.1 μm (particularly 0.01 to 0.1 μm).
It is preferably 1 μm, more preferably 0.05 to 0.1 μm).

The titanium oxide-adhered substrate according to the first aspect can be manufactured, for example, as follows. The substrate is immersed in an aqueous solution containing the fluorotitanium oxide or the like and the temperature is raised as necessary or the aqueous solution is applied to the substrate, and the deposited titanium oxide is adhered to the surface of the substrate, and thereafter. The titanium oxide-adhered substrate can be obtained by cooling, washing with water and drying.

As a method of immersing the base material in the aqueous solution,
As set forth in claim 2, the base material is an endless strip,
This base material can be moved by alternately and continuously moving the inside and outside of the aqueous solution. In this case, the titanium oxide can be uniformly attached to the base material, and a large area can be efficiently produced, which is preferable. Further, by making the concentration of the contained components in the aqueous solution constant, the titanium oxide can be uniformly attached to the base material. Therefore, it is preferable to circulate the aqueous solution to carry out this production.

The temperature for raising the temperature of the aqueous solution for depositing titanium oxide on the substrate can be appropriately selected according to the heat resistance of the substrate, but is preferably 20 to 100 ° C., more preferably 40 to 100 ° C. It is 70 ° C. Also, the temperature for drying the substrate can be appropriately selected depending on the heat resistance of the substrate. Further, this titanium oxide-adhered substrate is manufactured by a conventional processing machine for dyeing [normal pressure jet dyeing machine, wins, high pressure jet dyeing machine (FIG. 1, FIG. 15, FIG. 16 respectively).
[See])] or the like.

In the method for producing a curtain fabric base material according to claim 7, the curtain fabric base material having an endless belt is prepared by using a fluorotitanium complex compound, an alkaline agent, (1) malic acid or (2) malic acid and citric acid. It is characterized in that titanium oxide is deposited on the surface of the curtain material base material by alternately and continuously moving an aqueous solution containing an acid and the outside of the aqueous solution.

Examples of the above-mentioned "curtain material substrate" include those made of fibers such as wool, cotton, hemp, silk, rayon, acetate, acrylic and polyester. In addition, these may be woven or non-woven.
The thickness of the titanium oxide formed on the surface of the curtain fabric substrate is 0.001 to 0.1 μm (particularly 0.01 to 0.1 μm).
It is preferably 1 μm, more preferably 0.05 to 0.1 μm).

The above description can be applied to the "fluorotitanium complex compound" and the "alkali agent" as they are. The content of "(1) malic acid or (2) malic acid and citric acid" is 0.00 in the aqueous solution.
The amount is preferably 1 to 1 g / L (particularly 0.005 to 0.1 g / L, more preferably 0.01 to 0.05 g / L). When this content is less than 0.001 g / L, secondary aggregation of titanium oxide particles may be caused. On the other hand, this is 1g
If it exceeds / L, the titanium oxide particles may not be sufficiently precipitated.

As described in claim 8, the content of the fluorotitanium complex compound in the aqueous solution is 0.1.
˜30 g / L, the content of sodium hydrogen carbonate as the alkaline agent is 0.01 to 5 g / L, and the content of (1) malic acid or (2) malic acid and citric acid is 0.0.
It can be 01 to 1 g / L.

When titanium oxide is deposited, the temperature of the aqueous solution may be raised, and the temperature can be appropriately selected depending on the heat resistance of the curtain fabric base material, but is preferably 2.
The temperature is 0 to 100 ° C, more preferably 40 to 70 ° C. Further, the temperature for drying the curtain material base material can be appropriately selected according to the heat resistance of the curtain material base material. Further, the curtain fabric can be manufactured by using the above-mentioned processing machine or the like.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples. Example 1 (1) 5 parts of water was added to a dyeing tank 1 of a processing machine [a normal pressure jet dyeing machine, manufactured by Nissen Corporation, trade name "Swing Ace" (see FIG. 1)] of a titanium oxide-adhered substrate.
50 L is injected, and the base material 2 (100% wool suit fabric; width 156 cm, length 110 m, weight 29.8 kg (2 reciprocal parts)) is charged from the entrance / exit 3, and one end is connected to the other endless As a band, the reel 4 and the circulation pump 5
The base material was rotated by driving, and water was circulated by driving the circulation pump 5. Then, 1.5 kg of potassium titanium fluoride dissolved in hot water at 80 ° C. was poured into the injection tank 6
The solution was poured from above and left for 10 minutes to make the aqueous solution uniform. Next, as organic acids, citric acid 6 g and malic acid 6
g was injected from the injection tank 6 and left for 10 minutes. afterwards,
As an alkaline agent, 180 g of sodium hydrogen carbonate was injected from the injection tank 6, and water was added to the dyeing tank 1 until the total volume reached 600 L. At this time, the concentration of potassium titanium fluoride was 2.5 g / L, citric acid. Concentration of 0.01 g /
The concentration of L and malic acid was adjusted to 0.01 g / L, and the concentration of sodium hydrogen carbonate was adjusted to 0.3 g / L. next,
The temperature in the dyeing tank was raised to 65 ° C., and the temperature was maintained at 65 ° C. for 1 hour, then cooled, washed with water, and dried to obtain a titanium oxide-adhered substrate.

(2) Decomposition performance evaluation A test piece (about 18 cm × 18 cm) was prepared from Example 1, and as shown in FIGS. 2 and 3, a test piece storage with a chemiluminescent NOx meter connected to one end was stored. The test piece 11 was placed at the bottom of the container 10 [circular container (height 4 cm), internal volume: about 2 L], the light source 12 was a black light (15 W × 2, distance from container surface: 7 cm), and temperature was At 24 ± 2 ° C and 50% relative humidity, NOx gas (NO / N
O ₂ = about 98/2) 1 ppm was passed at a flow rate of 1 L / min for 30 minutes to perform a NOx gas decomposition test. The decomposition performance was evaluated by irradiating the light source and reducing the concentration of NOx gas. The results are shown in FIG. 4 [the double-headed arrow in the figure indicates the irradiation time of the light source (5 minutes per scale). (Note that the same applies to FIGS. 5 to 14 described later.)]. Further, Table 1 shows the average values for 10 to 20 minutes after irradiation with the light source. still,
Line A in the graph indicates the concentration of NOx in the container, line B indicates the concentration of NO in the container, and the difference between A and B is the concentration of NO ₂ (the concentration of NO ₂ contained from the beginning and NO The sum of NO ₂ concentrations in the middle stage of decomposition) is shown.

[0022]

[Table 1]

Example 2 100% polyester curtain cloth (width 15
0 cm, length 180 m, weight 30.6 kg (3 pieces)
A titanium oxide-adhered substrate was obtained in the same manner as in Example 1 except that was used. Using this, the same decomposition performance evaluation as in Example 1 was performed, and the results are shown in FIG. 5 and Table 1.
Further, the same test was conducted by replacing the light source with a fluorescent lamp (15 W × 2, distance from container surface: 7 cm), and the results are shown in FIG. 6 and Table 2. Further, for the fixing performance of titanium oxide to the base material, a part of the obtained titanium oxide-adhered base material was cut (100 × 150 cm), and washing was repeated 10 times under the following conditions, and the above decomposition performance test was conducted. Was evaluated. The results are shown in FIGS. 7 and 8 and Tables 1 and 2, respectively.

[0024]

[Table 2]

(Washing Conditions) Water having a liquid temperature of 40 ° C. was put to the top water level line of the water tank of the electric washing machine, and 2 kg of the synthetic detergent for clothes (JIS K 3371) was added to 1 L of the water.
Weak alkaline type 1) is added and dissolved to obtain a washing liquid. The base material of Example 2 is put into this washing liquid so that the bath ratio becomes 1:30, and the operation is started. After treating for 5 minutes, the operation is stopped, the above substrate is dehydrated by a dehydrator, and then the washing liquid is replaced with fresh water at room temperature, and rinsed with the same bath ratio for 2 minutes. After rinsing for 2 minutes, stop the operation, dehydrate the substrate, rinse again for 2 minutes,
Dehydrate and hang or flat dry without being affected by direct sunlight. Then, if necessary, dry iron finishing is performed at an appropriate temperature of the material fibers. The washing machine used for this washing is a household washing machine with a standard washing capacity and a standard water amount equipped with a centrifugal squeezing device conforming to the JIS C 9606 (electric washing machine) standard.

Comparative Example 1 The same base material as in Example 2 was used as it was to prepare a base material to which no titanium oxide was attached. Also, using this,
The same evaluations as in Example 2 were performed, and the results are shown in FIGS. 9 and 10 and Tables 1 and 2, respectively. However, the sticking performance was not evaluated.

Example 3 Substrate 2 (100% polyester curtain fabric; width 15)
0 cm, length 180 m, weight 30.6 kg (3 pieces)
Instead of the above, a titanium oxide-adhered base material was obtained in the same manner as in Example 1 except that the holding time at 65 ° C. was changed from 1 hour to 30 minutes. Using this, the same evaluation as in Example 1 was performed, and the results are shown in FIG. 11 and Table 3.

[0028]

[Table 3]

Example 4 Without adding citric acid, the amount of malic acid added was 12 g (0.0
A titanium oxide-adhered substrate was obtained in the same manner as in Example 3 except that 2 g / L) was used. Also, using this, Example 1
Evaluations similar to those were performed, and the results are shown in FIG. 12 and Table 3.

Example 5 Without adding malic acid, the amount of citric acid added was 12 g (0.0
A titanium oxide-adhered substrate was obtained in the same manner as in Example 3 except that 2 g / L) was used. Also, using this, Example 1
The same evaluation as above was performed, and the results are shown in FIG. 13 and Table 3.

Comparative Example 2 A titanium oxide-adhered substrate was obtained in the same manner as in Example 4 except that malic acid and citric acid were not added. Also, using this, the same evaluation as in Example 1 was performed, and the results are shown in FIG.
4 and Table 3.

Example 6 A 500 ml beaker was charged with 100 ml of water at 65 ° C., 0.5 g of potassium titanium fluoride and 0.005 of malic acid.
2 g, 0.002 g of citric acid and 0.06 g of sodium hydrogen carbonate were added, and then an aqueous solution was adjusted with water at 65 ° C. so that the liquid volume was 200 ml. Observation of the precipitation process of titanium oxide in this aqueous solution revealed that the colorless and transparent aqueous solution started to change its color to a candy color after 10 to 15 minutes, and with the passage of time while maintaining its transparency. The color became darker. After 25 to 30 minutes, it begins to turn white and cloudy 4.
After 5 minutes, the milky white color became strong, and colloidal particles became visible when light was applied to see through. After 60 minutes, it was found that the aggregated titanium oxide particles were precipitated.
On the other hand, except that malic acid and citric acid are not added,
An aqueous solution was prepared in the same manner as the above, and the precipitation process of titanium oxide in the aqueous solution was observed. As a result, the colorless and transparent aqueous solution began to become cloudy in white after 10 to 15 minutes. After minutes, the milky white color became stronger, colloidal particles became visible, and the aggregated titanium oxide particles were found to precipitate.

Effects of Examples According to FIGS. 4 to 10 and Tables 1 and 2, NOx decomposition was confirmed in Comparative Example 1 in which titanium oxide was not adhered, regardless of whether the light source of the apparatus was a black light or a fluorescent lamp. could not. On the other hand, in Example 1 in which the base material to which the titanium oxide was attached was wool, the NOx decomposition rate was 37.5% with black light, and excellent decomposition performance could be confirmed. Further, also in Example 2 in which the base material to which the titanium oxide is attached is polyester, excellent decomposition performance was confirmed, with a decomposition rate of 19.4% with black light and 11.6% with a fluorescent lamp. Moreover, what was washed 10 times of Example 2 was
The decomposition rate was 15.7% for black light and 9.0% for fluorescent lamps, confirming excellent decomposition performance equivalent to that before washing. From this, it can be seen that the titanium oxide of the titanium oxide-adhered base material produced by this method adheres strongly, and is excellent in durability performance and adhesion performance.

According to FIGS. 11 to 14 and Table 3, Comparative Example 2 containing no organic acid (citric acid and malic acid) was NO.
The decomposition rate of x was 9.2%. On the other hand, in Example 3 containing citric acid and malic acid, the decomposition rate was 11.9.
%, Example 4 containing malic acid without citric acid had 10.6%, and Example 5 containing citric acid without malic acid had 9.7%. from these things,
It was confirmed that an organic acid such as malic acid was involved in the adhesion of titanium oxide to the substrate and improved the decomposition performance.

In Example 6, when no malic acid and / or citric acid, which are organic acids, were contained, titanium oxide was immediately precipitated. On the other hand, when the organic acid such as malic acid was contained, it was confirmed that titanium oxide was gradually deposited. From these, by containing the organic acid, it is possible to control the deposition rate of titanium oxide, using an aqueous solution containing this organic acid,
When the titanium oxide-attached substrate is manufactured, fine and uniform titanium oxide particles can be attached and formed on the substrate.

It should be noted that the present invention is not limited to the above specific embodiments, but various modifications may be made within the scope of the present invention depending on the purpose and application. For example, when the base material is an endless strip or the like, in the production of the titanium oxide-adhered base material and the curtain fabric, it can be cut into a desired size after the titanium oxide is adhered and formed.
Further, the titanium oxide-adhered base material and the curtain material can be manufactured using a processing machine as shown in FIGS. 15 and 16.

[0037]

According to the manufacturing method of claims 1 and 7,
Regardless of the heat resistance of the base material, titanium oxide can be firmly formed on the base material with a uniform thickness, and in the decomposition of harmful substances,
It is possible to obtain a titanium oxide-adhered base material and a curtain material having excellent decomposition performance. Further, in the manufacturing method according to the seventh aspect, since the curtain fabric base material is the endless belt-like material, the titanium oxide can be more uniformly attached.

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing a processing machine (normal pressure jet dyeing machine) used for manufacturing Example 1.

FIG. 2 is an explanatory view seen from the front of the apparatus used for the NOx gas decomposition performance test.

FIG. 3 is an explanatory view seen from above of the apparatus used for the NOx gas decomposition performance test.

FIG. 4 is a graph showing the density when the light source of Example 1 is a black light.

FIG. 5 is a graph showing the density when the light source of Example 2 is a black light.

FIG. 6 is a graph showing the density when a light source of Example 2 is a fluorescent lamp.

FIG. 7 is a graph showing the density of a black light as a light source of Example 2 (after washing).

FIG. 8 is a graph showing the density of a fluorescent lamp as a light source in Example 2 (after washing).

FIG. 9 is a graph showing the density when the light source of Comparative Example 1 is black light.

FIG. 10 is a graph showing the density when a light source of Comparative Example 1 is a fluorescent lamp.

FIG. 11 is a graph showing the density when the light source of Example 3 is a black light.

FIG. 12 is a graph showing the density when the light source of Example 4 is a black light.

FIG. 13 is a graph showing the density when the light source of Example 5 is black light.

FIG. 14 is a graph showing the density when the light source of Comparative Example 2 is a black light.

FIG. 15 is an explanatory view schematically showing a processing machine (wins) usable in the present invention.

FIG. 16 is an explanatory view schematically showing a processing machine (high-pressure jet dyeing machine) usable in the present invention.

[Explanation of symbols]

1; dyeing tank, 2; substrate, 3; entrance / exit, 4; reel, 5;
Circulation pump, 6; injection tank, 7; transfer pipe, 8; heat exchanger,
9; nozzle, 10; test container, 11; test piece, 12; light source.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) D06M 10/00-11/84 F-term (4L031)

Claims (8)

(57) [Claims] 1. A substrate is immersed in an aqueous solution containing a fluorotitanium complex compound, an alkali agent and an organic acid, or the aqueous solution is applied to the substrate to deposit titanium oxide on the surface of the substrate. A method for producing a titanium oxide-adhered base material, comprising: 2. The method for producing a titanium oxide-adhered substrate according to claim 1, wherein the substrate is an endless belt, and the substrate is continuously moved alternately in the aqueous solution and outside the aqueous solution. . 3. The method for producing a titanium oxide-adhered substrate according to claim 1, wherein the organic acid is (1) malic acid or (2) malic acid and citric acid. 4. The content of the fluorotitanium complex compound in the aqueous solution is 0.1 to 30 g / L, and the content of sodium hydrogen carbonate as the alkaline agent is 0.01.
~ 5 g / L, the content of the above organic acid is 0.001-1 g / L
L is L, The manufacturing method of the titanium oxide adhesion base material in any one of Claims 1 thru | or 3. 5. The method for producing a titanium oxide-adhered substrate according to claim 1, wherein the substrate is a woven fabric. 6. The method for producing a titanium oxide-adhered substrate according to claim 1, wherein the woven fabric is made of wool fiber or polyester fiber. 7. A curtain fabric base material of an endless belt, a fluorotitanium complex compound, an alkali agent,
The aqueous solution containing (1) malic acid or (2) malic acid and citric acid and the outside of the aqueous solution are alternately moved continuously and immersed, and titanium oxide is added to the surface of the curtain fabric base material. A method for producing a curtain material, which comprises depositing. 8. The content of the fluorotitanium complex compound in the aqueous solution is 0.1 to 30 g / L, and the content of sodium hydrogen carbonate as the alkaline agent is 0.01.
The method for producing a curtain fabric according to claim 7, wherein the content of (1) malic acid or (2) malic acid and citric acid is 0.001 to 1 g / L.