JP3079766B2 - Manufacturing method of water-repellent, deep-colored fiber structure - 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 fibrous structure having excellent durability, water repellency and deep color performance.

[0002]

2. Description of the Related Art In recent years, demands for water repellency have been increasing mainly in the field of sports clothing and uniform clothing, and accordingly, there has been a strong demand for improving the level of water repellency in dry cleaning and washing.

At present, water repellency processing of cloth is performed by treating the cloth with fluorine or a silicone water repellent.

However, the silicone-based water repellent easily swells and dissolves in a solvent for dry cleaning, such as trichlene or perchrene, and the durability to dry cleaning is greatly reduced. Further, the water repellency of the silicone-based water repellent alone is low, and it is impossible to meet the recent demand for high water repellency.

On the other hand, the fluorine-based water repellent has a high initial level of water repellency, but since the resin film is hard and brittle, the resin film is cracked due to the fir action during washing or wearing, and the water repellency is reduced. However, none of them has been satisfactory with respect to recent high demands.

In a conventional water-repellent product made of fluorine or silicone resin, a methyl group or a fluorine-containing group contributing to water repellency penetrates into a resin film after a washing or dry cleaning step and the like. It had the serious disadvantage that performance was greatly reduced.

In the field of sports clothing and black formal, there is a strong demand for deep color and sharpness from the viewpoints of water repellency and fashionability, and various studies have been made.

[0008] Fluorine-based and silicone-based water-repellents generally used as water-repellent agents simultaneously cause deepening of the color, but as described above, there is a problem in the durability itself of the resin, so that the water-repellency is reduced. And the decrease in deep coloration occur simultaneously.

Many studies have been made on the deep coloration, especially with polyesters. Colloidal silica or the like is added to the polymer to create fine irregularities by reducing the alkali. However, in any case, irregularities on the fiber surface are crushed by a physical external force, so that the deep-colored property is reduced or the deep-colored unevenness is easily generated. Further, even if a fluorine-based or silicone-based water repellent is applied to such fibers, the durability of the resin is not improved, and none of the fibers has both durable water repellency and deep color.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a fabric having high water repellency, deep color, and excellent durability against washing or dry cleaning.

[0011]

The present invention has the following configuration to achieve the above object. That is, in the method for producing a water-repellent, deep-colored fiber structure of the present invention, after treatment with at least one of a fluorine-based and silicone-based water-repellent agent, treatment in an ozone atmosphere without drying, and drying. It is characterized by being treated with at least one of a fluorine-based and silicone-based water repellent, subjected to a corona discharge treatment without drying, and then dried.

[0012]

According to the present invention, a fibrous structure is treated with at least one of a fluorine-based and a silicone-based water repellent, and then subjected to ozone treatment in a wet state without drying, or corona discharge treatment, Thereafter, it has been found that the durability of the processing agent can be drastically improved when dried.

The fiber structure of the present invention is made of synthetic fibers and semi-synthetic fibers such as polyester, acrylic, nylon, acetate and rayon, natural fibers such as wool, cotton and silk, and mixtures thereof. It can be used for all knitted and woven fabrics, nonwoven fabrics, strings, tows, fibers and other structures irrespective of fibers and short fibers. As the fluorine-based water repellent of the present invention, a fluorine-based compound generally used as a water- and oil-repellent can be used. For example, polypentadecafluorooctyl acrylate, polytrifluoroethyl acrylate, tetrafluoroethylene- Fluorinated compounds such as hexafluoropropylene copolymers can be used.

As the silicone water repellent of the present invention, silicone compounds which are generally used as a water repellent, softener or leveling agent can be used. For example, dimethylpolysiloxane, a molecular terminal of dimethylpolysiloxane Alternatively, a polysiloxane compound modified by introducing a hydroxyl group, an amino group, an epoxy group, a polyether group, or the like into a side chain can be used.

These fluorine-based water repellents and silicone-based water repellents can be used alone or in combination of two or more. The processing agent is used in a state of being dissolved in an emulsion or a solvent. The method of applying such a processing agent to the fiber structure is not particularly limited as long as the cloth is treated by a padding method, an immersion method, or a spray method using a treatment liquid comprising the compound or the resin. .

According to the present invention, the fibrous structure subjected to such water repellent treatment is treated with ozone or corona discharge. With the ozone treatment of the present invention, a gas containing oxygen is used as a raw material, and ozone is supplied from an ozone producing apparatus using a corona discharge or a low-pressure mercury lamp to a treatment chamber to perform a predetermined treatment. A known device can be used as the ozone producing device. ◎ In such ozone treatment, for example, ozone is introduced into a processing chamber made of stainless steel or glass, and after controlling the ozone concentration to a predetermined value, the water-repellent cloth is guided to the processing chamber and treated for a predetermined time according to the purpose. do it. The concentration of ozone used in the present invention is preferably 500,000 to 100,000 ppm, more preferably 3 to 100 ppm.
000 to 100,000 ppm.

In the ozone treatment of the present invention, the ozone treatment atmosphere may be heated, preferably from 60 to 180.
° C, more preferably 100 to 150 ° C. The heating of the processing atmosphere may be performed by using a heating means such as a heater outside or inside the processing chamber, and is not particularly limited.

The corona discharge treatment of the present invention is generated by applying a high voltage between the electrodes under normal pressure, and either a direct current or an alternating current is used as a power source for applying the high voltage. be able to.

The electrodes for corona discharge treatment of the present invention include:
It is preferable to use an electrode composed of a high voltage application electrode and an earth electrode, wherein at least one of the electrodes is coated with a dielectric. Such a dielectric material, when in an electric field, does not allow movement of electric charges and has an increased electric capacity, and exhibits a so-called electrical insulating property. For example, rubber, glass,
It is preferable to use a material having sufficient withstand voltage against applied voltage, such as ceramic. The shape of the electrode is not particularly limited, and a plate shape, a roll shape, or the like can be used. Both electrodes are preferably cooled with water or the like as necessary. The distance between the two electrodes is 0.5 to 20 mm, preferably 1 to 5 mm.

The corona discharge treatment of the present invention is performed by exposing a wet fibrous structure provided with a water-repellent resin to a discharge portion generated between the electrodes. The gas in the discharge atmosphere is oxygen, air, or the like. Gases such as carbon monoxide, carbon dioxide, nitrogen, argon, and helium can be used alone or in combination of two or more.

After applying the fluorine-based and / or silicone-based water repellent of the present invention, ozone treatment or corona discharge treatment in a wet state without drying is performed, and then drying is performed. The effect that the property is dramatically improved is achieved.

The fluorine-based water repellent and the silicone-based water repellent of the present invention form a uniform film-like resin layer on the fiber surface, and it is considered that the film-like resin layer has a crosslinked structure.

The water repellent agent of the present invention may contain a crosslinking agent, an antistatic agent, a softening agent, and a hard finish as long as the effects of the present invention are not excluded.

[0024]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition,
The performance values shown in Examples and Comparative Examples were measured by the following methods.

(Water repellency) Measured by a test method (spray method) specified in JIS-L-1079.

(Coloring property) The L value was measured by a digital colorimetric color difference calculator (manufactured by Suga Test Instruments Co., Ltd.). The L value is an index of the luminous density of a color, and a smaller value indicates a deeper color.

(Washing durability) 0.2% of 40 ° C. ± 2 ° C. in an automatic reversing spiral electric washing machine (VH1150 type manufactured by Toshiba Corporation)
A step of adding a weakly alkaline synthetic detergent (defined in JIS-K-337), adjusting the bath ratio to 1:50, washing under strong conditions for 10 minutes, and then draining and washing with water for 5 minutes is one step. This was repeated 20 times and air-dried.

(Dry Cleaning Durability) A dry cleaning cylinder (a cylinder having a diameter of about 22 cm and a length of about 33 cm, which is 45 to 45 degrees around an axis inclined by 50 ° from the axis of the cylinder)
3.8 l of room temperature perchlorethylene was added to the mixture (rotating at 50 rpm), 230 g of test cloth was added thereto, and the process of rotating for 10 minutes was performed once. This was repeated 20 times and then air-dried.

Examples 1 to 7 and Comparative Examples 1 to 7 A cashmere doskin woven fabric using 75 denier 36 filaments for the warp and 100 denier 36 filaments for the weft (both polyester processed yarns manufactured by Toray Industries, Inc.) was scoured by a conventional method and heat-treated. Set, then Dianix Black BG-FS (Disperse dye manufactured by Mitsubishi Chemical Corporation) 15
The dyeing was carried out at 135 ° C. for 45 minutes at a concentration of% owf, then reduced, washed with water, dried and heat-set at 170 ° C. by a conventional method. The black dyed fabric was treated under the following conditions, and the performance was evaluated. The results are shown in Table 1.

(Water Repellent Processing) A: After dipping in an aqueous solution containing 20 g / l of NK Guard FG270 (a fluorine-based water repellent and oil repellent manufactured by Nikka Chemical Co., Ltd.), wet pick-up becomes 80% with a mangle. Squeezed.

B: The same as A was dried at a temperature of 130 ° C. (Ozone treatment) Ozone generator: Corona discharge method (source gas: oxygen) Ozone concentration: (a) 3,000 ppm, (b) 10,000 ppm Treatment temperature: (A) 25 ° C, (A) 100 ° C Ozone After the treatment, A was dried at 130 ° C and then heat-treated at 180 ° C, and B was heat-treated at 180 ° C. B was heat-treated at 180 ° C. without ozone treatment, and Comparative Example 6 was obtained.

[0032]

[Table 1] From Table 1, it can be seen that those of Examples 1 to 7 have both excellent water repellency and color developing performance with higher durability than those of the comparative examples. After the water-repellent treatment of the comparative example, the dried and then ozone-treated ones, when the processing conditions become strong,
As a matter of course, the initial water repellency level was lowered due to the cleavage of the fluorine bonding group of the resin or the formation of the hydrophilic group, and it was not possible to produce a highly water-repellent cloth.

Example 8 and Comparative Example 8 In Example 1, 20 g / l of NK Guard FG270 (a fluorine-based water and oil repellent manufactured by Nika Chemicals Co., Ltd.) was added, and Drypon 600 (a silicone-based oil-repellent manufactured by Nika Chemicals Co., Ltd.) was used. Water-repellent) is immersed in an aqueous solution having a concentration of 5 g / l, squeezed with a mangle so as to obtain a wet pickup of 80%, treated with ozone, then dried at 130 ° C. and heat-treated at 180 ° C. The same processing as in Example 1 was performed.

The ozone treatment was performed in the same apparatus as in Example 1, using an ozone concentration of 15,000 ppm, a treatment temperature of 30 ° C., and a treatment time of 20 seconds. In Comparative Example 8, after being squeezed with a mangle as in Example 8, dried at 130 ° C. and heat-treated at 180 ° C. Table 2 shows the results of evaluating the performance of the obtained woven fabric.

[0035]

[Table 2] It can be seen that the product according to the present invention has both excellent water-repellent performance and color-developing property.

Examples 9 to 12 and Comparative Examples 9 to 13 The same black woven fabric as in Example 1 was treated under the following conditions, and the performance was evaluated. The results are shown in Table 3.

(Water-repellent treatment) C: NK Guard FGN700 (a fluorine-based water-repellent and oil-repellent agent manufactured by Nichika Chemical Co., Ltd.) and Sumitex Resin M-3 (melamine resin manufactured by Uchiyu Chemical Co., Ltd.) 20/4 g / l 80% wet pick-up after immersion in an aqueous solution adjusted to a concentration of
After squeezing with a mangle so as to obtain a corona discharge, the mixture was dried at 130 ° C. and heat-treated at 180 ° C.

D: After squeezing with a mangle as in C, 13
It was dried at 0 ° C and heat-treated at 180 ° C. (Corona discharge treatment) Electrode: Both the discharge electrode and the ground electrode are coated with silicone rubber on a metal roll and placed at a distance of 4 mm between the electrodes. Both rolls rotate at a speed of 5 m / min. Discharge power source: discharge frequency 30 KHz, discharge power 1 KW Treatment method: A sample was attached to a ground electrode, and the number of treatments was changed.

[0039]

[Table 3] It can be seen that those of Examples 9 to 12 have both durable water repellency and deep color. In the case where the number of treatments in the comparative example was increased, the initial water repellency level was reduced due to cleavage of the fluorine bonding group of the resin and formation of the hydrophilic group.

[0040]

According to the present invention, it is possible to provide a fiber structure having high water repellency and high deep color, which is excellent in washing resistance and dry cleaning resistance.

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Claims (2)

(57) [Claims] 1. A water-repellent, deep-water treatment comprising treating a fiber structure with at least one of a fluorine-based and silicone-based water-repellent agent, treating the fiber structure in an ozone atmosphere without drying, and then drying. A method for producing a colored fiber structure. 2. A water-repellent, deep-color, which comprises treating a fiber structure with at least one of a fluorine-based and silicone-based water-repellent agent, subjecting the fiber structure to a corona discharge treatment without drying, and then drying. Method for producing a conductive fiber structure.