JPH0533269A - Flameproofing method for cellulosic fiber cloth - Google Patents

Abstract

(57) [Summary] [Objective] The present invention uses an amidophosphazene compound in which aluminum chloride, which is economically inseparable, remains mixed with cellulose, and is advantageous industrially and without lowering the strength of the cellulosic fiber cloth. A method for flameproofing a fiber-based fabric is provided. [Structure] Cellulose fiber cloth is represented by the general formula: It is characterized by treating with a solution containing an amidophosphazene compound (wherein m is 3 or more), ammonium chloride, and sodium trichloroacetate. Further, the cellulosic fiber cloth is treated with a solution containing an alkaline substance, and then the general formula: It is characterized in that it is treated with a solution containing an amidophosphazene compound of the formula (m is 3 or more) and ammonium chloride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for flameproofing a cellulosic fiber cloth using amidophosphazene containing ammonium chloride.

[0002]

2. Description of the Related Art In recent years, various methods have been used to impart flameproofness to cellulosic fiber cloths. For example, APO (Tris 1 aziridinyl
Phosphine oxide), Fy from Stoufa Chemical
rol FR-2 (Tris ・ 1.3 ・ cycloisopropyl phosphate), G.I. L. Martin's TRIS
(Tris ・ 2.3 ・ dibromopropyl phosphate), Provrane processing method of Albright & Wilson (mainly using tetrakishydroxyoxyphosphonium sulfate), Pyrovatex CP (N-methyloldimethylphosphonopropionamide) of Ciba-Geigy ), A method using amidophosphazene, etc. are known. And APO, Fyrol FR-2, TR
IS is no longer used due to toxicity problems, and at present, the Provan processing method, the Pyrovatex CP method and the amide phosphazene method are generally used to impart flame resistance to the cellulosic fiber cloth.

However, the Provan processing method is a method in which a condensation compound of tetrakishydrooxyphosphonium sulfate and urea is used as a flameproofing agent and is treated with ammonia gas. Therefore, a separate facility for treating with ammonia gas is required and the processing cost is high. There is a problem of being expensive. On the other hand, the Pyrovatex CP method adjusts a high-concentration liquid such as Pyrovatex CP, melamine resin, and catalyst and applies it to the fabric, so the stability of the adjustment liquid is not good and the flameproof performance is not stable, and in the drying process There is a problem that the work environment is not good due to the generation of formalin odor. A flameproofing method using an amidophosphazene compound is disclosed in US Pat. No. 2,782,782.
Many proposals have been made in Japanese Patent No. 133, etc., and it is known that formalin is not generated and durable flameproofness can be imparted.

The above-mentioned amidophosphazene compound is obtained by the reaction of a chlorophosphazene compound and ammonia, but ammonium chloride is obtained in a large amount as a by-product. However, since the amidophosphazene compound and ammonium chloride have similar properties to a solvent and cannot be easily separated industrially, the current situation is that the amidophosphazene compound and ammonium chloride are commercially available in a mixed form. .

However, when flameproofing treatment is performed using an amidophosphazene compound in which ammonium chloride remains mixed, ammonium chloride is dissociated in the heat treatment step,
There is a problem that generated hydrogen chloride reduces the strength of the cellulosic fiber.

In order to solve these problems, JP-A-61-296177 discloses a method of treating a cellulosic fiber cloth with a solution containing an amidophosphazene compound, ammonium chloride and an alkaline substance. Although it has been proposed, the stability of the processing bath is poor and the processing bath separates, and the problem that the amide phosphazene compound decomposes due to the reaction heat when ammonium chloride reacts with the alkali and a sufficient flameproof effect cannot be obtained. There is.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is industrially advantageous by using an amidophosphazene compound in which ammonium chloride, which cannot be economically separated, remains mixed. Moreover, an object of the present invention is to provide a method for flameproofing a cellulosic fiber cloth without reducing the strength of the cellulosic fiber cloth.

[0008]

In order to achieve the above object, the present invention has the following constitution. That is, the first aspect of the present invention is based on the general formula of cellulosic fiber cloth.

[Chemical 3] A method for flameproofing a cellulosic fiber cloth is characterized in that it is treated with a solution containing an amidophosphazene compound (wherein m is 3 or more), ammonium chloride, and sodium trichloroacetate. The second invention is to treat a cellulosic fiber cloth with a solution containing an alkaline substance, and then to give a compound of the general formula

[Chemical 4] A gist is a flameproofing method for a cellulosic fiber cloth, which comprises treating with a solution containing an amidophosphazene compound (wherein m is 3 or more) and ammonium chloride.

The present invention will be described in detail below.

The cellulosic fiber cloth referred to in the present invention includes woven fabrics, knitted fabrics and non-woven fabrics containing at least 50% or more of cellulosic fibers such as cotton and hemp and / or regenerated cellulose fibers such as viscose rayon and copper ammonia rayon. To be

The amidophosphazene compound used in the present invention is

[Chemical 5] (In the formula, m is 3 or more), and specifically, m = 3.
Hexaamidophosphazene (cyclic trimer) and m = 4
Octamidophosphazene (cyclic tetramer) and the like. The amidophosphazene compound contains ammonium chloride as a reaction by-product. The amount of amidophosphazene used varies depending on the type of cellulosic fiber, the mixing ratio other than the cellulosic fiber, its type, and the required performance.
It is preferred to deposit the active ingredient in a proportion of -20% by weight. That is, if it is less than 1% by weight, the flameproof effect cannot be obtained, and if it exceeds 20% by weight, it is not economical for its effect. Then, a known reaction accelerator or softening agent may be added to the amide phosphazene compound.

Specific examples of the sodium trichloroacetate used in the present invention include Remazol Salt FD (manufactured by Hoechst Co., Ltd.), and the amount used is chlorine in a mixture of amidophosphazene and ammonium chloride. Almost equivalent amounts of ions are suitable.

Examples of the alkaline substance used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium trichloroacetate and the like. A suitable amount of such alkaline substance is about the equivalent of chloride ions in the mixture of amidophosphazene and ammonium chloride.

When simultaneously applying the amidophosphazene compound, ammonium chloride, and sodium trichloroacetate, a pad-dry-bake method or the like is used. The heat treatment is preferably performed at 150 to 190 ° C. for 1 to 5 minutes. When the heat treatment temperature is low, the treatment time becomes long, while when the heat treatment temperature is high, the treatment time becomes short, but at a high temperature, the deterioration of the cellulose fiber is large, which is not preferable. Then, it is washed with hot water and dried to obtain a flameproof product.

First, when applying an alkaline substance to a cellulosic fiber cloth, a pad-dry method or the like is used.
Next, when applying the amidophosphazene compound and ammonium chloride to the cellulosic fiber cloth, a pad-dry-bake method or the like is used. The heat treatment condition is 150 ~
It is preferable to carry out at 190 ° C. for 1 to 5 minutes. Then, it is washed with hot water and dried to obtain a flameproof product.

[0016]

EXAMPLES The present invention will be described in detail below based on examples.

The flameproofness was evaluated in accordance with the Fire Service Agency Notification No. 11 after washing 5 times and then JIS L-10.
A combustion test was conducted by the A-1 method (heated with a 45 ° micro-burner for 1 minute) specified in 91.

The tear strength was determined by the D method (Pendulum method) specified in JIS L-1096.

Example 1 A cotton flat fabric having a warp density of 16 yarns / inch and a weft yarn density of 60 yarns / inch using 20 count single yarn as the warp yarn and 100 count yarn as the weft yarn is wicked, desizing and scouring by a conventional method. , Bleached, mercerized.

The plain woven fabric was treated with amide phosphazene AA-1000 (manufactured by Nippon Soda Co., Ltd., active ingredient 42%, ammonium chloride 58%) as an amide phosphazene compound.
Containing) 400 g / l, Apinone 301 as a reaction accelerator
(Manufactured by Sanwa Chemical Co., Ltd.) 100 g / l, Remazol Salt FD (manufactured by Hoechst Co., Ltd., active ingredient 98%) 30 g / l as sodium trichloroacetate, and water in a bath It was dipped and the pickup rate was reduced to 70%. Then, after drying at 120 ° C. for 1 minute, baking was performed at 150 ° C. for 3 minutes. Then, this treated cloth was washed with hot water at 60 ° C. for 5 minutes and dried to obtain the product of Example 1 of the present invention.

Example 2 Using the same material as in Example 1, Remazol Salt FD
Was treated in the same manner as in Example 1 except that the amount was changed to 50 g / l to obtain a product of Example 2 of the present invention.

Comparative Example 1 Using the same material as in Example 1, Remazol Salt FD
The same treatment as in Example 1 was carried out except that was not used to obtain a product of Comparative Example 1.

Comparative Example 2 Using the same material as in Example 1, Remazol Salt FD
The product of Comparative Example 2 was obtained by performing the same treatment as in Example 1 except that 15 g / l of sodium hydroxide was used instead of 30 g / l.

Comparative Example 3 Using the same material as in Example 1, Remazol Salt FD
A product of Comparative Example 3 was obtained by performing the same treatment as in Example 1 except that 20 g / l of soda ash was used instead of 30 g / l.

Example 1, Example 2, Comparative Example 1, Comparative Example 2
And the state of the treatment liquid of Comparative Example 3, the tear strength of the obtained product, the flameproof property after 5 times of washing, and the treatment liquids of each Example and Comparative Example, which were obtained after being used for 24 hours. Table 1 shows the tear strength and the flameproof property after 5 washings of the obtained product.

[0026]

[Table 1]

As is clear from Table 1, the products obtained in the examples of the present invention are excellent in tear strength and flameproof performance.

EXAMPLE 3 The plain weave of the mercerized fabric of Example 1 was dipped in a treatment solution prepared by adjusting Remazol Salt FD 50 g / l as sodium trichloroacetate and water in one bath, and picking up a pick-up rate of 70.
%, Dried at 120 ° C. for 1 minute, and pretreated.

This pretreated plain woven fabric was treated with amide phosphazene AA-1000 40 as an amide phosphazene compound.
0 g / l, 100 g of Apinone 301 as a reaction accelerator
/ L, Ult latex FSA as a silicone softener
(Ciba Geigy Co., Ltd.) 30 g / l, and water was immersed in a treatment solution (pH 7.3) adjusted to one bath, and the pickup rate was reduced to 70%. And after drying for 1 minute at 120 ℃,
Baking at 150 ° C. for 3 minutes. This treated cloth is then 6
It was washed with hot water at 0 ° C for 5 minutes and dried to obtain the product of Example 3 of the present invention.

Example 4 Remazol salt FD was prepared using the same material as in Example 3.
Was treated in the same manner as in Example 3 except that the amount was changed to 100 g / l to obtain a product of Example 4 of the present invention.

Example 5 Using the same dough as in Example 3, the same treatment as in Example 3 was carried out except that 50 g / l of sodium hydrogencarbonate was used in place of remazol salt, and Example 5 of the present invention was applied. Got the product.

Comparative Example 4 A product of Comparative Example 4 was obtained by using the same fabric as in Example 3 and carrying out the same treatment as in Example 3 except that the pretreatment was not performed.

Table 2 shows the tear strength of the products obtained in Examples 3, 4 and 5, and Comparative Example 4 and the flameproof property after 5 times of washing.

[0034]

[Table 2]

As is clear from Table 2, the products obtained in the examples of the present invention were excellent in tear strength and flameproof performance.

[0036]

As described in detail above, the fabric treated by the method of the present invention exhibits a flameproofing effect with extremely good washing resistance, a small tear strength reduction, and interior products such as curtains and working materials. It is useful for clothing such as clothes, sheets, pajamas, and bedding. Further, it is very useful for industrial production without any drawbacks such as high processing cost.

Claims (2)

[Claims] 1. A cellulosic fiber cloth is represented by the general formula: A flameproofing method for a cellulosic fiber cloth, which comprises treating with a solution containing an amidophosphazene compound (wherein m is 3 or more), ammonium chloride and sodium trichloroacetate. 2. A cellulosic fiber cloth is treated with a solution containing an alkaline substance, and then the general formula: A flameproofing method for a cellulosic fiber cloth, which comprises treating with a solution containing an amidophosphazene compound (wherein m is 3 or more) and ammonium chloride.