JPH073641A - Improved antiflaming treatment of polyamides - Google Patents

Abstract

PURPOSE:To obtain natural and synthetic polyamide fibers with excellent wash resisting antiflaming property, by treating them with a specific treating agent. CONSTITUTION:Natural and synthetic polyamide fibers are treated with an aqeous acid solution consisting of a treating solution containing a substituted phthalic acid with one or more chlorine or bromine atoms and its derivatives, together with a chromium compound (for example: bichromates), and an added inorganic acid (or an organic acid); or first treated with an aqueous acid solution of a halogenated phthalic acid, and then treated with an aqueous acid solution containing the chromium compound (or visa versa) to give excellent wash resisting antiflaming property.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for imparting flameproofness excellent in washing durability to natural or synthetic polyamide fibers.

[0002]

BACKGROUND ART As a technique for imparting flameproofness to wool or the like, a method in which a complex salt of titanium or zirconium is adsorbed on fibers in an acidic solution is well known. Although it is possible to process it with a certain amount of flame, the flameproof performance is gradually reduced by repeated washing. Further, this method cannot give satisfactory flameproof performance to nylon, feathers and the like.

As a technique for compensating for the drawbacks of the above processing, as disclosed in JP-A-3-32876, there has been proposed a method in which a fluoride of titanium or zirconium is used in combination with tetrabromophthalic acid.

[0004]

However, in this technique, nylon, feathers and the like including wool can be provided with sufficient flameproof performance at the stage of processing, but the durability to washing is weak and repeated washing with water is required. The flameproof performance gradually deteriorates, and various test standards cannot be passed.

The present invention improves on the above-mentioned drawbacks of the prior art,
It is intended to provide a flameproof treatment method having excellent washing durability for many polyamide fibers such as wool, feathers, animal hair, silk and nylon.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies and have studied natural or synthetic polyamide fibers with respect to phthalic acid substituted with at least one chlorine or bromine atom and its derivative (hereinafter referred to as phthalic acid). By treating halogenated phthalic acid and its derivative pair) together with a chromium compound in an acidic solution, it is possible to obtain a high level of flameproofness and excellent washing durability that could not be obtained with conventional techniques. I discovered that it can be realized.

The treatment of the fibers according to the invention has to be carried out in an acidic aqueous solution. It is necessary to treat the treatment liquid with a pH of 1.0 to 6.0, but a pH of 2.0 to 4.0 is preferable in consideration of treatment efficiency and fiber damage. Inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid can be used as the substance that makes the pH of the treatment liquid acidic, but organic acids such as formic acid, acetic acid, oxalic acid, and citric acid can also be used.

The flameproof treatment of the present invention can be carried out by simultaneously treating the fiber with halogenated phthalic acid and its derivative and a chromium compound. Further, the fiber is previously treated with phthalic acid and its derivative which have been halogenated in an acidic aqueous solution, and then treated with a chromium compound in an acidic aqueous solution, and
The reverse processing method is also possible.

In the flameproof treatment according to the present invention, the treatment temperature is 30.
The treatment can be performed at ˜130 ° C., but the treatment at a high acidity and a high temperature causes a large damage to the polyamide fibers. However, when treated at a low temperature, the adsorption of the drug to the fiber is slow, and the reaction with the fiber is not sufficiently completed, so that the washing durability is deteriorated. Therefore, from the viewpoint of processing efficiency, the temperature of the processing liquid is preferably 60 to 100 ° C.

The halogenated phthalic acid and its derivative used in the present invention are mono-, di-, tri-, tetra-bromo obtained by brominating phthalic anhydride or mono-, di-, tri-, tetra-chloro obtained by chlorination. It is also possible to use phthalic anhydride, various alkali and metal salts of halogenated phthalic acid obtained by hydrolyzing these, or various esters and amides of halogenated phthalic acid. The amount of the halogenated phthalic acid and its derivative used in the present invention is about 1 to 100% owf (% by weight of the drug with respect to the weight of the fiber), although it depends on the amount of the chromium compound used.

The chromium compound of the present invention is chromate, dichromate, potassium alum, chromic chloride, basic chromium sulfate, chromic sulfate, chromic nitrate, chromic acetate, etc., The amount used is 0.1-20% owf
Is.

The fibers applicable to the present invention are of synthetic and natural polyamide type. As synthetic polyamide fibers, nylon (nylon 6, nylon 11, nylon 66, etc.) and as natural polyamide fibers are JIS.
L 0204 is the hair (wool, animal hair, feathers, etc.) described in Section 3, 3 and the silk etc. described in Section 3.4.

[0013]

[Function] Polyamide fibers are cationized in an acidic aqueous solution, and the halogenated phthalic acid and its derivative of the present invention and a chromium compound form a strong complex in the acidic aqueous solution. By exhibiting a high degree of washing durability that could not be obtained, and by using both halogenated phthalic acid and its derivative and a chromium compound together, the flameproof performance is synergistically improved. Presumed.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples. (Example 1) Tetrabromophthalic acid disodium salt was added to 1
The pH of the treatment bath prepared at a ratio of 5% owf, potassium dichromate 4% owf and a bath ratio of 1:20 was 2.
Adjust to 0. After commercially available wool furano fabric was added to this treatment liquid, the temperature of the treatment liquid was raised from room temperature to about 100 ° C., treated at this temperature for 30 minutes, and then the treated cloth was thoroughly washed with water and dried. With respect to the wool furano fabric obtained by the above treatment, the flameproof performance before and after washing with water was measured. The washing conditions were based on the Fire Service Agency Notification No. 1, “Standard of washing resistance performance related to flameproof performance” dated February 21, 1986, but a neutral detergent was used as the detergent. Further, the evaluation of the flameproof performance was carried out by a flame test method of a polymer material according to JIS L-1091 A-4 method 12 seconds flame contact and JIS K 7201 oxygen index method. The test results are shown in Table 1.

[Table 1]

(Example 2) Treatment was carried out using tetrabromophthalic anhydride under the same conditions as in Example 1. The test results for flameproof performance are shown in Table 1.

[Table 1]

(Example 3) Treatment was carried out using tetrachlorophthalic anhydride under the same conditions as in Example 1. The test results for flameproof performance are shown in Table 1.

[Table 1]

(Example 4) 4% of potassium dichromate was added.
The pH of the treatment bath having wf and a bath ratio of 1:20 is adjusted to 2.0 with dilute sulfuric acid. The same wool furano fabric as in Example 1 was added to this treatment liquid, the temperature was raised from room temperature to about 100 ° C., treated at this temperature for 30 minutes, and then cooled to room temperature. Subsequently, 15% owf disodium tetrabromphthalate was added to the same treatment bath, pH was adjusted to 2.0 again with dilute sulfuric acid, treated under the same temperature conditions as above, washed with water and dried. The obtained treated cloth was evaluated for flameproof performance under the same conditions as in Example 1. The results are shown in Table 1.

[Table 1]

(Embodiment 5) The procedure was the reverse of that of Embodiment 4. First, 15% owf of tetrabrom phthalic acid disodium salt was added to the treatment bath having a bath ratio of 1:20, and the pH of the treatment bath was adjusted to 3.0 with phosphoric acid.
Adjust to. The same wool furano fabric as in Example 1 was added to this treatment liquid, the temperature was raised from room temperature to about 100 ° C., treated at this temperature for 30 minutes, and then cooled to room temperature. Subsequently, 4% owf of potassium dichromate was added to the same treatment bath, PH was adjusted to 3.0 again with phosphoric acid, treated under the same temperature conditions as above, washed with water and dried. The obtained treated cloth was evaluated for flameproof performance under the same conditions as in Example 1. The results are shown in Table 1.

[Table 1]

Example 6 The same procedure as in Example 1 was carried out except that chromium alum was used as the chromium compound. The results are shown in Table 1.

[Table 1]

(Example 7) Tetrabromophthalic acid disodium salt 20% owf, potassium dichromate 5% o
After adjusting the pH of the treated liquid having a wf of 1:20 with formic acid to 3.5, commercially available nylon taffeta was added. The temperature of the processing solution is raised from room temperature to about 100 ° C, and at this temperature, 30
After being treated for a minute, the dough was thoroughly washed with water and dried. The washing conditions were the same as in Example 1. The flameproof performance was evaluated by the 45 degree coil method based on Article 4-3 of the Fire Service Act Enforcement Order. The results are shown in Table 2.

[Table 2]

(Embodiment 8) In exactly the same manner as in Embodiment 7,
Nylon jersey was used, and the same treatment conditions were used. The results are shown in Table 2.

[Table 2]

(Example 9) Tetrabromophthalic acid disodium salt 25% owf, potassium dichromate 4% o
wf, bath ratio 1:40, pH of this treated solution is 2.0 with acetic acid
Down to 50% down in this treatment liquid.
Feather (50%) is added and the temperature of the processing liquid is changed from room temperature to 70
The temperature was raised to 0 ° C., and treatment was performed at this temperature for 30 minutes. After the treatment, the feathers were thoroughly washed with water and dried. The evaluation of the flameproof performance of the obtained feathers was performed by washing with water under the same conditions as in Example 1 and then using the 45 ° mesenamine basket method. The results are shown in Table 3.

[Table 3]

(Embodiment 10) Down 70%, Feather 3
Feathers having a composition of 0% were used and treated under the same conditions as in Example 9. The results are shown in Table 3.

[Table 3]

(Comparative Example 1) After adjusting the pH of the treatment liquid having 20% owf of potassium zirconium fluoride and the bath ratio of 1:20 to 2.0 with dilute sulfuric acid, wool furano ground was added and the temperature was raised from room temperature to 75 ° C. The temperature was raised, treated at this temperature for 30 minutes, washed with water and dried. The flameproof performance was evaluated by the same method as in Example 1. The results are shown in Table 1.

[Table 1]

(Comparative Example 2) The pH of a treatment solution of potassium zirconium fluoride 20% owf, tetrabromophthalic acid 15% owf, and a bath ratio of 1:20 was adjusted to 2.0 with dilute sulfuric acid, and then the wool furano material was used. Is added, the temperature is raised from room temperature to 75 ° C., treated at this temperature for 30 minutes, washed thoroughly with water,
Dried. The flameproof performance was evaluated by the same method as in Example 1. The results are shown in Table 1.

[Table 1]

(Comparative Example 3) Tetrabromophthalic acid 15%
After adjusting the pH of the treatment liquid with owf and bath ratio 1:20 to 2.0 with dilute sulfuric acid, add wool furano ground, raise the temperature from room temperature to 75 ° C., treat for 30 minutes at this temperature and wash well with water. , Dried up. The flameproof performance was evaluated by the same method as in Example 1. The results are shown in Table 1.

[Table 1]

(Comparative Example 4) Zirconium fluoride potassium 20% owf, tetrabrom phthalate disodium 2
After adjusting the pH of the treatment solution having 0% owf and the bath ratio of 1:15 to 2.0 with dilute sulfuric acid, nylon taffeta is added and the temperature is raised from room temperature to 75 ° C. for 30 minutes. Then, it was washed with water and dried. The flameproof performance was evaluated in the same manner as in Example 7. The results are shown in Table 2.

[Table 2]

(Comparative Example 5) Zirconium fluoride potassium 20% owf, tetrabrom phthalate disodium 25
% Owf, pH of the treatment liquid of 1:40 bath ratio was diluted with dilute sulfuric acid.2.
After adjusting to 0, the same feathers as used in Example 9 are put in, the temperature is raised from room temperature to 75 ° C., and the treatment is performed for 30 minutes. Then, it was washed with water and dried. The evaluation of flameproof performance was performed by the same method as in Example 9. The results are shown in Table 3.

[Table 3]

[0029]

The results of the examples clearly show that they are superior to the comparative examples. Therefore, the natural and synthetic polyamide fibers treated according to the present invention have extremely low deterioration of flameproof performance even after repeated washing with water, and have high flameproofness as compared with those treated by the conventional method. Since it can be used, it can be used in various fields.

Claims (4)

[Claims] 1. A phthalic acid substituted with at least one chlorine or bromine atom or a derivative thereof, and a treatment liquid containing a chromium compound added to a natural or synthetic polyamide fiber, and an inorganic acid or an organic acid is added thereto. An improved flameproof treatment method for polyamide fibers, which comprises treating in an acidic aqueous solution. 2. A natural or synthetic polyamide fiber is treated in an acidic aqueous solution containing halogenated phthalic acid and its derivative, and then a treatment liquid containing a chromium compound is added with an inorganic acid or an organic acid. An improved method for flameproofing polyamide fibers, characterized by treating in an acidic aqueous solution. 3. A natural or synthetic polyamide fiber is treated in an acidic aqueous solution containing a chromium compound, and then a treatment solution containing halogenated phthalic acid and its derivative is treated with an inorganic acid or an organic acid. An improved flameproof treatment method for polyamide fibers, which comprises treating in an added acidic aqueous solution. 4. The chromium compound is treated with chromic acid, dichromic acid, potassium alum, chromic chloride, basic chromic sulfate, chromic sulfate, chromic nitrate, chromic acetate, etc. An improved flameproof treatment method for polyamide fibers, comprising: