JPH08260357A - Water-repelling processing - Google Patents

Abstract

PURPOSE: To provide a method for subjecting a wool-containing fabric to a water-repelling processing rich in washing durability by imparting a sulfonated bisphenol S-formaldehyde condensate to the wool-containing fabric, further imparting a resin composition containing a water-repelling fluorinated agent to the treated fabric, and subsequently thermally treating the fabric. CONSTITUTION: A method for subjecting a fabric to a water-repelling processing comprises subjecting the blend fabric of wool with polyester fibers, etc., to the exhaustion treatment of a sulfonated bisphenol S-formaldehyde condensate of the formula (n is 0-3) in the same dyeing machine as that used for dyeing the fabric, washing the fabric, drying the fabric, padding the fabric with a treating composition comprising a water-repelling fluorinated agent, a melamine resin and a multifunctional blocked isocyanate group-containing urethane resin, subjecting the treated fabric to an intermediate drying treatment, and subsequently thermally treating the fabric.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water repellent finishing method. More specifically, the present invention relates to a water-repellent finishing method which is excellent in washing durability of a fabric containing wool fibers.

[0002]

2. Description of the Related Art Conventionally, as a water repellent treatment for a cloth, a method has been generally used in which a cloth containing a fluorine-based water repellent is impregnated with the cloth, and then the mangle is squeezed, dried and heat treated.

However, there is a problem that even if a small amount of wool fiber is contained in the cloth, the laundry durability of the cloth treated in this way is significantly lowered.

In order to improve the washing durability, it is necessary to add a large amount of a fluorine-based water repellent, but since the texture becomes coarse and hard, some proposals have been made to prevent this.

Japanese Unexamined Patent Publication No. 61-680 discloses an exhaustion method of immersing a fluorine-based water repellent in an aqueous dispersion. But,
In this case, a thin film is formed and a soft texture is obtained, but the durability is insufficient.

Further, in Japanese Patent Application Laid-Open No. 60-162871, after a fluorine-based water repellent is applied, it is treated with an organic solvent solution of acrylic resin, urethane resin, silicone resin, etc. 2
A step method is disclosed. However, in this case, it is necessary to perform two types of treatments, that is, an aqueous system and a solvent system, which complicates the process.

Japanese Patent Laid-Open No. 1-92483 discloses a method of applying a fluorine-based water repellent after treating with low temperature plasma. However, in this case, the process is complicated, such as processing in a vacuum container.

After all, none of these proposals has been able to perform a water-repellent treatment with a soft texture having sufficient washing durability on the fabric containing wool.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, that is, provides a water repellent processing method with a soft texture having sufficient washing durability for a fabric containing wool. This is an issue.

[0010]

In order to solve the above problems, the method of the present invention has the following constitution. That is, after applying a formalin condensate of sulfonated bisphenol S to a fabric containing wool fibers, a treatment liquid in which a fluorine-based water repellent, a melamine resin and a urethane resin containing a polyfunctional blocked isocyanate group are mixed is applied and heat treated. Is a water-repellent finishing method.

The method of the present invention will be described in more detail below.

The fibers used in the method of the present invention include wool fibers. If the wool fiber is not contained, the above-mentioned problems do not occur in the water repellent treatment.

Here, the wool fiber includes wool, cashmere, camel hair, and alpaca hair.

In the method of the present invention, a formalin condensate of sulfonated bisphenol S is applied before the water repellent treatment. Without this step, it is difficult to apply a water-repellent finish having a soft texture with sufficient washing durability.

Although the reason for this is not clear, the surface of the wool fiber is a hydrophobic epicuticle layer, and since it is difficult to wet, it has poor penetrability of the water repellent processing liquid and poor adhesion to the water repellent. It is presumed that by adding the formalin condensate of sulfonated bisphenol S, the wetting property is greatly improved, and thus the water repellency and the adhesiveness with the wool fiber are significantly improved.

The formalin condensate of sulfonated bisphenol S preferably has, for example, the structure of the following general formula [I], and from the viewpoint of improving solubility in water and preventing gelation, It is preferable that n is 0 to 3.

[0017]

Embedded image The amount of the sulfonated bisphenol S formalin condensate applied to the weight of the cloth is sufficient to impart sufficient washing durability, while the texture is hard and the treated cloth is prevented from discoloring. 0.05 ~ 4
It is preferable to set it to be wt%, further 0.1 to 2 wt%.

The formalin condensate of sulfonated bisphenol S is preferably used in the form of an aqueous solution, and a pH adjusting agent such as maleic acid, hydrochloric acid, sulfuric acid or formic acid is used to adjust the pH to 2 to 6,
Further, it is preferable to adjust the pH to 3 to 4, and a bath ratio of 1:20 to 1:50, a temperature of 40 to 80 ° C., and further 5
The temperature is preferably 0 to 70 ° C. Processing time is 5-40
Minutes, more preferably 10 to 30 minutes. In the present invention, it is usually washed with water and dried after the treatment with the aqueous solution.

Next, a treatment liquid containing a fluorine-based water repellent, a melamine resin, and a urethane resin containing a polyfunctional blocked isocyanate group is applied to the cloth and heat-treated. As a method of applying, a method of padding and then drying is preferable.

The fluorine-based water repellent may be any one having a perfluoroalkyl group, for example, AG-95.
5 (manufactured by Asahi Glass Co., Ltd.), AG-970 (manufactured by Asahi Glass Co., Ltd.), Dickguard F-90 (Dainippon Ink and Chemicals, Inc.)
Manufactured). In addition to these, a silicone-based soft water repellent may be used in combination, and a fluorine-based water repellent such as Drypon 600 (manufactured by Nichika Kagaku Co., Ltd.) prevents the texture from becoming coarse and hard. On the other hand, from the viewpoint of obtaining sufficient washing durability, it is preferable to add 0.01 to 10 wt%, more preferably 0.03 to 5 wt% in terms of solid content to the weight of the fabric.

The melamine resin can be selected from various melamines from trimethylolmelamine to hexamethylolmelamine.

When the melamine resin is used in a large amount, the crosslinking effect is improved, but the texture tends to be effective. From the viewpoint of maintaining a soft texture while obtaining a sufficient cross-linking effect, it is preferable to add 0.01 to 2 wt%, and further 0.02 to 1 wt% in terms of solid content to the weight of the fabric.

As a melamine curing catalyst, ammonium phosphate, ammonium sulfate, ammonium nitrate, aluminum phosphate, aluminum sulfate, aluminum nitrate,
Inorganic acid salts such as zinc phosphate, zinc sulfate, zinc nitrate, ammonium formate, ammonium acetate, ammonium acrylate, ammonium succinate, aluminum formate, aluminum acetate, aluminum acrylate, aluminum succinate, zinc formate, zinc acetate, acrylic It is also preferable to use an organic acid salt such as zinc acid salt or zinc succinate together.

For the polyfunctional blocked isocyanate group-containing urethane resin, an organic compound containing two or more blocked isocyanate functional groups in the molecule can be used. Specific examples include the following compounds. That is, tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, hydrogenated diphenyl methane diisocyanate, triphenyl triisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, trimethylol propane tolylene diisocyanate, glycerin tolylene diisocyanate, etc., dissociate during heating. There is a compound in which an isocyanate group is blocked by reacting phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ε-caprolactam, etc., in which an active isocyanate group is regenerated.

Usually, the polyfunctional blocked isocyanate group-containing urethane resin is used as a water-dispersed liquid in which a small amount of a surfactant is blended and forcibly emulsified.

When a polyfunctional blocked isocyanate group-containing urethane resin is used in a large amount, the crosslinking effect is improved, but there are problems such as a texture effect, thermal yellowing during processing, and reduction in dyeing fastness. From the viewpoint of preventing these problems while obtaining a sufficient cross-linking effect, the solid content is 0.01 to 4 wt%, further 0.03 to the fabric weight.
It is preferable to add 1 wt%.

In the present invention, a treatment liquid obtained by mixing a fluorine-based water repellent, a melamine resin and a urethane resin containing a polyfunctional blocked isocyanate group is applied to the cloth to be treated and heat treated. Without heat treatment, water-repellent finish with washing durability cannot be applied. Before heat treatment, usually 80
It is preferable to perform drying at about 130 ° C. for about 10 seconds to 3 minutes. Next, preferably 140 to 180 ° C., 30 seconds to 5
The heat treatment is performed under the condition of minutes.

[0028]

The present invention will be described below in detail with reference to examples.

The test methods used in the examples are as follows.

Washing method (20 times washing method): 45 cm × 4
A test cloth of 5 cm was sampled and the weight of the other cloth was 80.
Adjust to 0 g. Toshiba Co., Ltd. automatic reversing spiral electric washing machine VH-1150 type electric washing machine with the same performance as a washing tub of 40 ± 2 ℃ slightly 0.2% alkaline synthetic detergent (JIS 3371 weak alkaline type 1) Aqueous solution 2
Add 5 liters and a test cloth and wash for 25 minutes under strong conditions. Transfer the test cloth to a centrifugal dehydrator and spin it for about 30 seconds, then transfer it to a washing tub filled with water at room temperature.
Rinse for 0 minutes. After dehydration for about 30 seconds again, rinse under the same conditions for 10 minutes.

After repeating this step four times, it is air-dried.
This was after 20 washes.

Water repellency: According to JIS L 1092 (spray method).

(Example 1) 55 wt% polyester fiber
%, 45 wt% wool blended fabric (tropical, warp:
No. 60 twin yarn 56 / inch, weft: No. 30 single yarn 56 / in
ch)) to dyeing with normal processing affirmation, and then using the same dyeing machine used for dyeing, solidify Dimafix ES (manufactured by Meisei Chemical Co., Ltd.), which is a formalin condensate of sulfonated bisphenol S. 1.2 wt% in minutes, and a bath ratio of 1: with a treatment liquid adjusted to pH 3.0 with acetic acid.
The treatment was carried out at 20 at 70 ° C. for 20 minutes. Then wash with water and dry, pad the resin solution of the following formulation with a pickup of 60%, dry at 110 ° C for 2 minutes, and at 170 ° C for 1 minute.
Curing (heat treatment) was performed for a minute.

[Resin formulation] Fluorine-based water repellent: AG-970 (Asahi Glass Co., Ltd.) 80 g / l Melamine resin: Sumitex Resin M-3 (Sumitomo Chemical Co., Ltd.) 3 g / l Organic amine salt system Catalyst: Sumitex Accelerator ACX (manufactured by Sumitomo Chemical Co., Ltd.) 1 g / l Polyfunctional blocked isocyanate group-containing urethane resin: Super Fresh JB-7300 (manufactured by Kyoshinkasei Co., Ltd.) 5 g / l The sample had a soft texture.
The evaluation results of this water repellency are shown in Table 1. It had excellent water repellency even after 20 washes.

[0035]

[Table 1] Comparative Example 1 Dimafix ES (Meisei Chemical Co., Ltd.), which is a formalin condensate of sulfonated bisphenol S
Table 1 also shows the evaluation results of the water repellency of the sample obtained by performing the same treatment as in Example 1 except that the treatment in (manufacturing) was omitted.

(Comparative Example 2) The evaluation results of the water repellency of the sample obtained by treating in the same manner as in Example 1 except that the water repellent treatment was carried out under the condition that the melamine resin was excluded in the resin formulation were shown in Table 1.
Are also shown.

(Comparative Example 3) A sample obtained by treating in the same manner as in Example 1 except that the water repellent treatment was carried out under the condition that the urethane resin containing a polyfunctional blocked isocyanate group was excluded from the resin formulation. The results of the aqueous evaluation are also shown in Table 1.

[0038]

Industrial Applicability According to the method of the present invention, a fabric containing wool fibers can be imparted with a water-repellent performance having a soft texture and excellent durability.

Claims (2)

[Claims] 1. A fabric containing wool fibers is provided with a formalin condensate of sulfonated bisphenol S, and then a treatment liquid prepared by mixing a fluorine-based water repellent, a melamine resin and a urethane resin containing a polyfunctional blocked isocyanate group is applied. A water-repellent finishing method characterized by heat treatment. 2. A formalin condensate of sulfonated bisphenol S has a structure of general formula [I], where n is 0 to 0.
3. The water-repellent finishing method according to claim 1, wherein the water-repellent finishing method is 3. Embedded image