Method for manufacturing titanium oxide-adhered base material and curtain cloth

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a method for producing a titanium oxide-adhered base material and a curtain fabric. More specifically, the present invention is excellent in that titanium oxide can be firmly formed on the base material with a uniform thickness regardless of the heat resistance of the base material. The present invention relates to a method for producing a titanium oxide-adhered base material and a curtain fabric having decomposition performance of harmful gases and the like. INDUSTRIAL APPLICABILITY The present invention is used for manufacturing interior fabrics such as curtains, chair upholstery, wallpaper, clothing fabrics, industrial materials, and the like.

【0002】

[Conventional technology]

Conventionally, a photocatalytic function such as titanium oxide has been used for the purpose of decomposing harmful substances. Most of these are titanium oxides formed on the surface of the base material by a sol-gel method, a vacuum vapor 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 adhesiveness is not sufficient and the titanium oxide or the like is peeled off or dropped off with some friction. At present, it has occurred and a sufficient photocatalytic function has not been obtained.

【0003】

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

【0004】

[Problems to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and can firmly form titanium oxide on a base material with a uniform thickness regardless of the heat resistance of the base material, and is a harmful substance [nitrogen oxide, sulfur oxidation. An object of the present invention is to provide a method for producing a titanium oxide-attached base material and a curtain cloth having excellent decomposition performance in the decomposition of air (gas) containing harmful substances such as substances, aldechts, pathogens, and molds]. And.

【0005】

[Means for solving problems]

The method for producing a titanium oxide-adhered base material according to claim 1 is to immerse the base material in an aqueous solution containing a fluorotitanium complex compound, an alkaline agent and an organic acid, or apply the aqueous solution to the base material, and then apply the base material to the base material. It is characterized by depositing titanium oxide on the surface of the material.

【0006】

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

【0007】

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

【0008】

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

【0009】

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

【0010】

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

【0011】

The thickness of the titanium oxide formed on the surface of the base material is preferably 0.001 to 0.1 μm (particularly 0.01 to 0.1 μm, more preferably 0.05 to 0.1 μm).

【0012】

The titanium oxide-adhered base material according to claim 1 can be produced, for example, as follows. The base material is immersed in the aqueous solution containing the fluorotitanium oxide or the like and the temperature is raised as necessary, or the aqueous solution is applied to the base material to attach the precipitated titanium oxide to the surface of the base material, and then. , Cooled, washed with water and dried to obtain a titanium oxide-attached substrate.

【0013】

As a method of immersing the base material in the aqueous solution, as shown in claim 2, the base material may be an endless strip, and the base material may be continuously moved alternately inside and outside the aqueous solution. .. In this case, the titanium oxide can be uniformly adhered to the base material, and a large area can be efficiently produced, which is preferable. Further, since the titanium oxide can be uniformly adhered to the base material by keeping the concentration of the contained component in the aqueous solution constant, it is preferable to circulate the aqueous solution to carry out this production.

【0014】

The temperature for raising the temperature of the aqueous solution when the titanium oxide is precipitated on the base material can be appropriately selected depending on the heat resistance of the base material, but is preferably 20 to 100 ° C, more preferably 40 to 70 ° C. C. Further, the temperature at which the base material is dried can be appropriately selected according to the heat resistance of the base material. Further, the production of this titanium oxide-adhered base material is performed by a conventional processing machine for dyeing [normal pressure liquid flow dyeing machine, wins, high pressure liquid flow dyeing machine (see FIGS. 1, 15, and 16 respectively)] and the like. It can also be done using.

【0015】

The method for producing a curtain fabric base material according to claim 7 comprises using an endless strip-shaped curtain fabric base material with a fluorotitanium complex compound, an alkaline agent, and (1) malic acid or (2) malic acid and citric acid. It is characterized in that the inside of the contained aqueous solution and the outside of the aqueous solution are alternately and continuously moved and immersed to precipitate a titanium oxide on the surface of the curtain cloth base material.

【0016】

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

【0017】

The above description can be applied as it is to the above-mentioned "fluorotitanium complex compound" and the above-mentioned "alkaline agent". The content of the above "(1) malic acid or (2) malic acid and citric acid" is 0.001 to 1 g / L (particularly 0.005 to 0.1 g / L, and further 0.01 to 0.05 g / L) in the above aqueous solution. It is preferable to do so. If this content is less than 0.001 g / L, secondary aggregation of titanium oxide particles may occur. On the other hand, if this exceeds 1 g / L, titanium oxide particles may not be sufficiently precipitated.

【0018】

As shown in claim 8, the content of the fluorotitanium complex compound in the aqueous solution is 0.1 to 30 g / L, the content of sodium hydrogen carbonate as the alkaline agent is 0.01 to 5 g / L, and the above (1). The content of) malic acid or (2) malic acid and citric acid can be 0.001 to 1 g / L.

【0019】

When the titanium oxide is precipitated, the temperature of the aqueous solution may be raised, and the temperature can be appropriately selected depending on the heat resistance of the curtain cloth base material, but is preferably 20 to 100 ° C, more preferably 20 to 100 ° C. It is 40 to 70 ° C. Further, the temperature at which the curtain fabric base material is dried can also be appropriately selected according to the heat resistance of the curtain fabric 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

Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 (1) Preparation of titanium oxide-attached base material Inject 550L of water into the dyeing tank 1 of the processing machine [normal pressure liquid flow dyeing machine, manufactured by Nissen Co., Ltd., trade name "Swing Ace" (see Fig. 1)], and base material 2 (100% wool suit fabric; width; 156 cm, length 110 m, weight 29.8 kg (2 pieces) is thrown in from the doorway 3, one end and the other end are connected to form an endless strip, and the reel 4 and the circulation pump 5 are driven. The base material was rotated and water was circulated by driving the circulation pump 5. Then, 1.5 kg of potassium titanium fluoride dissolved in boiling water at 80 ° C. was injected from the injection tank 6 and left for 10 minutes to make the aqueous solution uniform. Next, as organic acids, 6 g of citric acid and 6 g of malic acid were injected from the injection tank 6 and left for 10 minutes. After that, 180 g of sodium hydrogen carbonate was injected from the injection tank 6 as an alkaline agent, 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 and citric acid. The acid concentration was adjusted to 0.01 g / L, the citric acid concentration to 0.01 g / L, and the sodium hydrogen carbonate concentration to be 0.3 g / L. Next, the temperature in the dyeing tank was raised to 65 ° C., held at 65 ° C. for 1 hour, cooled, washed with water, and dried to obtain a titanium oxide-attached substrate.

【0021】

(2) Evaluation of disassembly performance 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 container 10 [circular container (height 4 cm)) to which a chemiluminescent NOx meter was connected to one end. ), Internal volume: Approximately 2 L] Place the test piece 11 on the bottom, set the light source 12 to black light (15 W x 2, distance to the container surface: 7 cm), temperature 24 ± 2 ° C, relative humidity 50 %, NOx gas (NO / NO) from the other end₂= Approximately 98/2) A NOx gas decomposition test was conducted by passing 1 ppm at a flow rate of 1 L / min for 30 minutes. The decomposition performance was evaluated by irradiating a light source and reducing the concentration of NOx gas. This result is shown in Fig. 4 [The double-headed arrow in the figure indicates the irradiation time of the light source (1 scale 5 minutes). (The same applies to FIGS. 5 to 14 described later.)]. Furthermore, Table 1 shows the average value for 10 minutes from 20 to 30 minutes after irradiation with a light source. The line A in the graph shows the concentration of NOx in the container, the line B shows the concentration of NO in the container, and the difference between A and B is NO.₂Concentration (NO included from the beginning)₂NO in the middle of being oxidized and decomposed₂The sum of the concentrations of) is shown.

【0022】

[table 1]

<img file="JP2002138366A_D0001.tif" />【0023】

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

【0024】

[Table 2]

<img file="JP2002138366A_D0002.tif" />【0025】

(Washing conditions) Pour water with a liquid temperature of 40 ° C up to the water level line at the top of the water tank of the electric washing machine, and add 2 kg of water to 1 L of water. Seeds) are added and dissolved to make a washing liquid. The base material of Example 2 is added to the washing liquid so that the bath ratio is 1: 30, and the operation is started. After the treatment for 5 minutes, the operation is stopped, the base material is dehydrated with a dehydrator, then the washing liquid is replaced with fresh water at room temperature, and the washing is performed at the same bath ratio for 2 minutes. After rinsing for 2 minutes, stop operation, dehydrate the substrate, rinse again for 2 minutes, dehydrate and hang or lay flat without being affected by direct sunlight. Then, if necessary, dry iron finish at an appropriate temperature of the material fiber. The washing machine used for this washing is a household washing machine with a standard washing capacity and a standard amount of water with a centrifugal squeezing device that conforms to the JIS C 9606 (electric washing machine) standard.

【0026】

Comparative example 1 The same base material as in Example 2 was used as it was, and a base material to which titanium oxide was not attached was used. Moreover, using this, the same evaluation as in Example 2 was performed, and the results are shown in FIG. 9, FIG. 10, Table 1 and Table 2, respectively. However, the sticking performance was not evaluated.

【0027】

Example 3 Implemented except that the base material 2 was replaced with (100% polyester curtain fabric; width 150 cm, length 180 m, weight 30.6 kg (3 pieces)) and the holding time at 65 ° C was changed from 1 hour to 30 minutes. A titanium oxide-attached substrate was obtained in the same manner as in Example 1. 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]

<img file="JP2002138366A_D0003.tif" />【0029】

Example 4 A titanium oxide-attached base material was obtained in the same manner as in Example 3 except that citric acid was not added and the amount of malic acid input was changed to 12 g (0.02 g / L). Moreover, using this, the same evaluation as in Example 1 was performed, and the results are shown in FIG. 12 and Table 3.

【0030】

Example 5 A titanium oxide-attached base material was obtained in the same manner as in Example 3 except that malic acid was not added and the input amount of citric acid was changed to 12 g (0.02 g / L). Moreover, using this, the same evaluation as in Example 1 was performed, and the results are shown in FIG. 13 and Table 3.

【0031】

Comparative example 2 A titanium oxide-attached base material was obtained in the same manner as in Example 4 except that malic acid and citric acid were not added. Moreover, using this, the same evaluation as in Example 1 was performed, and the results are shown in FIG. 14 and Table 3.

【0032】

Example 6 In a 500 ml beaker, put 100 ml of 65 ° C water, 0.5 g of potassium titanium fluoride, 0.002 g of malic acid, 0.002 g of citric acid and 0.06 g of sodium hydrogen carbonate, and then 65 ° C so that the liquid volume becomes 200 ml. The aqueous solution was prepared with the water of. When the precipitation process of titanium oxide in this aqueous solution was observed, the color of the aqueous solution, which was colorless and transparent, began to change to a light brown color after 10 to 15 minutes, and with the passage of time while maintaining the transparency. The color became darker. After 25 to 30 minutes, it began to become cloudy white, and after 45 minutes, it became milky white, and colloidal particles became visible when exposed to light. After 60 minutes, agglomerated titanium oxide particles were observed to precipitate. On the other hand, except that malic acid and citric acid were not added, the aqueous solution was prepared in the same manner as above, and the precipitation process of titanium oxide in this aqueous solution was observed. After ~ 15 minutes, the color of the aqueous solution began to turn white and turbid, and after 20 minutes, the milky white color became stronger, colloidal particles became visible, and aggregated titanium oxide particles were observed to precipitate.

【0033】

Effect of Examples According to FIGS. 4 to 10, Tables 1 and 2, in Comparative Example 1 in which titanium oxide was not attached, NOx decomposition could not be confirmed regardless of whether the light source of the apparatus was a black light or a fluorescent lamp. On the other hand, in Example 1 in which the base material to which the titanium oxide was attached was wool, the decomposition rate of NOx was 37.5% with black light, and excellent decomposition performance was confirmed. Furthermore, in Example 2 in which the base material to which the titanium oxide was attached was polyester, excellent decomposition performance was confirmed, with a decomposition rate of 19.4% for black light and 11.6% for fluorescent lamp. In addition, when Example 2 was washed 10 times, the decomposition rate was 15.7% for black light and 9.0% for fluorescent lamp, confirming the same excellent decomposition performance as before washing. From this, it can be seen that the titanium oxide of the titanium oxide-attached base material produced by this method is firmly adhered, and is excellent in durability performance and fixing performance.

【0034】

According to FIGS. 11 to 14 and Table 3, in Comparative Example 2 containing no organic acid (citric acid and malic acid), the decomposition rate of NOx was 9.2%. On the other hand, Example 3 containing citric acid and malic acid had this decomposition rate of 11.9%, and Example 4 containing no citric acid and containing malic acid had this 10.6%, and citric acid without citric acid was used. In Example 5, which included, this was 9.7%. From these facts, it was confirmed that an organic acid such as malic acid is involved in the adhesion of the titanium oxide to the substrate and improves the decomposition performance.

【0035】

Further, in Example 6, when the organic acids malic acid and / or citric acid were not contained, the titanium oxide was immediately precipitated. On the other hand, when an organic acid such as malic acid was contained, it was confirmed that titanium oxide was gradually precipitated. From these facts, the precipitation rate of titanium oxide can be adjusted by containing an organic acid, and if a titanium oxide-attached base material is produced using an aqueous solution containing this organic acid, it will be fine. Uniform titanium oxide particles can be adhered and formed on the substrate.

【0036】

In addition, the present invention is not limited to the above-mentioned specific examples, and various modifications can be made within the scope of the present invention according to the purpose and application. For example, in the production of a titanium oxide-adhered base material and a curtain fabric when the base material is an endless strip or the like, it can be cut to a desired size after the titanium oxide adhered and formed. Further, these titanium oxide-adhered base materials and curtain fabrics can also be produced by using a processing machine as shown in FIGS. 15 and 16.

【0037】

[Effect of the invention]

According to the production methods according to claims 1 and 7, titanium oxide can be firmly formed on the base material with a uniform thickness regardless of the heat resistance of the base material, and titanium has excellent decomposition performance in the decomposition of harmful substances. Oxide-attached base materials and curtain fabrics can be obtained. Further, in the production method according to claim 7, the titanium oxide can be adhered more uniformly by using the curtain fabric base material as an endless strip.

[Simple explanation of drawings]

[Figure 1]

It is explanatory drawing which shows typically the processing machine (atmospheric pressure liquid flow dyeing machine) used for manufacturing of Example 1.

[Figure 2]

It is explanatory drawing seen from the front direction of the apparatus used for the decomposition performance test of NOx gas.

[Fig. 3]

It is explanatory drawing which looked at from the upper direction of the apparatus used for the decomposition performance test of NOx gas.

[Fig. 4]

It is a graph which shows the density | density | concentration at the light source of Example 1.

[Fig. 5]

It is a graph which shows the density | density | concentration at the light source of Example 2 | black light.

[Fig. 6]

It is a graph which shows the density | concentration in the light source of Example 2 | fluorescent lamp.

[Fig. 7]

It is a graph which shows the density | density | concentration at the light source of Example 2 (after washing) with a black light.

[Fig. 8]

It is a graph which shows the density | concentration in the light source of Example 2 (after washing) with a fluorescent lamp.

[Fig. 9]

It is a graph which shows the density | density | concentration at the light source of the comparative example 1 with a black light.

[Fig. 10]

It is a graph which shows the density | density | concentration at the light source of the comparative example 1 | fluorescent lamp.

[Fig. 11]

It is a graph which shows the density | density | concentration at the light source of Example 3. black light.

[Fig. 12]

It is a graph which shows the density | density | concentration at the light source of Example 4 | black light.

[Fig. 13]

It is a graph which shows the density | density | concentration at the light source of Example 5. black light.

[Fig. 14]

It is a graph which shows the density | density | concentration at the light source of the comparative example 2 is a black light.

[Fig. 15]

It is explanatory drawing which shows typically the processing machine (wins) which can be used for this invention.

[Fig. 16]

It is explanatory drawing which shows typically the processing machine (high pressure liquid flow dyeing machine) which can be used for this invention.

[Explanation of symbols]

1; Staining tank, 2; Base material, 3; Doorway, 4; Reel, 5; Circulation pump, 6; Injection tank, 7; Transfer tube, 8; Heat exchanger, 9; Nozzle, 10; Test container, 11; Specimen, 12; Light source.