JPS589194B2 - Flame retardant treatment method for cellulose fiber structures - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for durable flame retardant treatment of cellulose fiber structures.

It has been known for a long time that phosphorus is effective in making fibrous structures generally flame retardant, especially cellulose fibrous structures, and tetrakishydroxymethylphosphonium chloride (TH
PC), those based on tetrakis hydroxymethylphosphonium hydroxide (THPOH), etc., N
-Methylo-lyredimethylphosphonopropionamide, vinyl phosphate oligomer, etc. are introduced.

However, although these processing agents have excellent durability, they have drawbacks such as high price, odor during processing, messy processing methods, hardening of the fibers after processing, instability of the chemicals, and decreased physical properties. However, it has not been widely put into practical use.

Also known is a method of introducing phosphorus into fiber molecules using phosphorous acid or its derivatives.

According to this known method, by setting appropriate reaction conditions, cellulose can be easily converted to phosphite in a short time, and there is no hardening after treatment, and the texture of the treated fabric is good. The flame retardant effect was also good.

However, it had the drawback of insufficient durability such as washing resistance.

In view of the above conventional methods, the present inventors focused on a flame retardant treatment method using phosphorous acid or its derivatives, which is expected to be versatile due to improved durability such as washing resistance, and worked diligently to eliminate its drawbacks. As a result of research, the present invention was arrived at. By reacting a cellulose fiber structure with a phosphorus compound and then treating it with guanidine or its derivative, there is almost no hardening after treatment and no decrease in strength. The present invention provides a flame retardant treatment having many features such as good workability and excellent durability such as washing resistance.

That is, the present invention relates to the following general formula (wherein X represents -OH).

) In the flame retardant treatment of cellulose fiber structures using phosphorus compounds shown in It is.

When cellulose fiber structures are treated with phosphorous acid or its derivatives, the high reactivity of phosphorous acid or its derivatives causes an esterification reaction with the hydroxyl groups in the molecules of the cellulose fiber structures in a short time and efficiently, resulting in phosphorus. is chemically introduced, resulting in high flame retardancy.

However, when the flame-retardant cellulose fiber structure obtained by this method is washed at home using a commercially available synthetic detergent, its flame retardancy rapidly decreases.

Although the cause of the rapid decline in flame retardancy is not Sada,
An ion exchange reaction occurs between the sodium component in the commercially available synthetic detergent, the hydroxyl group in the molecule of the cellulose fiber structure, and a portion of the esterified phosphorous acid or its derivatives. This is thought to be due to the formation of sodium salts of its derivatives.

The present inventors have conducted extensive studies on various chemicals and agents, and have found that guanidine or its derivatives have been developed for the purpose of protecting phosphorous acid or its derivatives that have undergone an esterification reaction with the hydroxyl groups in the molecules of cellulose fiber structures. Its durability has been improved by substantially post-processing.

The reason why durability is improved by post-treatment to impart guanidine or its derivatives is that by performing a wall post-treatment that is not guanidine, the hydroxyl groups in the molecules of the cellulose fiber structure undergo an esterification reaction. Chemical reactions such as addition reactions occur with phosphoric acid or its derivatives, protecting the phosphorous acid or its derivatives, and inhibiting ion exchange reactions with sodium components in commercially available synthetic detergents, resulting in reduced durability. It is thought that the characteristics have improved.

As the phosphorus compound represented by the general formula used in the present invention,
In addition to phosphorous acid, mention may be made of ammonium phosphite, methylphosphonate, ammonium methylphosphonate, phenylphosphonate, ammonium phenylphosphonate, ethylphosphonate, and ammonium ethylphosphonate.

In addition to guanidine, guanidine or its derivatives include methylolated guanidine, dicyandiamide, methylolated dicyandiamide, monomethyl dicyandiamide, monoethyl dicyandiamide, monopropyl dicyandiamide, monoisopropyl dicyandiamide, monomethylol monomethyl dicyandiamide, dimethylol monomethyl dicyandiamide, Trimethylol monomethyl dicyandiamide, monomethylol monoethyl dicyandiamide, dimethylol monoethyl dicyandiamide, trimethylol monoethyl dicyandiamide, monomethylol monopropyl dicyandiamide, dimethylol monopropyl dicyandiamide, trimethylol monopropyl dicyandiamide, monomethylol monoisopropyl dicyandiamide, di Examples include methylol monoisopropyl dicyandiamide and trimethylol monoisopropyl dicyandiamide.

Further, the substantial post-treatment of guanidine or its derivatives in the present invention means treatment in all steps after the cellulose fiber structure is treated with a phosphorus compound represented by the general formula. Continuous application methods include, in addition to the commonly used bat method, a spray method using a sprayer, and a coating method using various coaters. The continuous application method requires post-application heat treatment, which includes, in addition to the commonly used hot full type dry heat treatment, infrared radiant heat treatment using infrared rays, and induction high-frequency heat treatment using microwaves. .

On the other hand, as a batch application treatment method, there is a method of immersing the material in a treatment bath maintained at a constant temperature for a certain period of time.

The present invention will be explained in detail in the following examples.

In addition, flame retardancy, washing method, bending resistance, and tear strength in Examples were measured as follows.

(1) Flame retardancy Flame retardancy was determined by JIS L 1091-1971 A-1 method and heating for 1 minute (45° microburner method).

In this case, Category 3 is charred area of 30cm2 or less, afterflame time of 3
The residual dust time is 5 seconds or less.

(2) Washing method: Use a tumbler type household electric washing machine (manufactured by Toshiba).
50 g of commercially available synthetic detergent New Beads (manufactured by Kao Sekiken) was added to 30 liters of hot water at 0° C., and one washing operation was performed for 10 minutes.

(3) Bending resistance: According to JIS L 1004-1972A method (45° cantilever method).

Usually, when this value is in the range of 35 to 55, a desirable texture is given.

(4) Tear strength: Determined by JIS L 1004-1972C method (pendulum method).

The tear strength of the unprocessed fabric was expressed as 100.

Example (1) After immersing a scouring and bleached cotton cloth (basis weight 110 g/m2) in the following treatment bath, it was subjected to mangle squeezing (squeezing ratio 70%) and then 1
Curing was performed at 50° C. for 3 minutes, and then soaping was performed at 80° C. for 5 minutes in a soaping bath containing 5 g/l of a nonionic surfactant.

Next, drying was performed at 100° C. for 2 minutes. Treatment bath Ammonium phosphite 120 parts Dimethylformamide 880 parts Then, as a post-treatment, it was immersed in the following treatment bath at a temperature of 90°C for 5 minutes to obtain a flame-retardant cotton fabric.

Treatment bath Dimethylol monoethyl dicyandiamide 200 parts Water 800 parts For reference, the treated fabric up to the post-treatment in the above-mentioned treatment steps was taken as Comparative Example (1).

Table 1 shows the results of flame retardant performance, bending resistance, and tear strength of Example (1), Comparative Example (1), and the unprocessed fabric.

As is clear from Table 1, in the case of the method of the present invention, there is little deterioration in physical properties, and excellent durability is observed in which the flame retardant performance does not deteriorate rapidly due to washing.

Example (2) and Example (3) Same cotton cloth as used in Example (1) (fabric weight 1109/m2
) in the following treatment bath and squeezed with a mangle (squeezing rate 8
0%), then heat-treated using an induction high-frequency device,
Thereafter, soaping was performed at 80° C. for 5 minutes in a soaping bath containing 5 g/l of a nonionic surfactant.

Next, drying was performed at 100° C. for 2 minutes.

Treatment bath Methyl phosphonate 150 parts Thiourea 210 parts Pyridine 83 parts Water 557 parts Next, as a post-treatment, it was immersed in the following treatment bath and squeezed with a mangle (squeezing ratio 7).
Example (2) was obtained by drying at 100° C. for 90 seconds.

Further, Example (3) was obtained by further performing dry heat treatment at 150° C. for 2 minutes after drying in Example (2).

Treatment bath Monomethylol guanidine 60 parts water
Comparative Example (2) was 940 parts of Example (2) without any post-treatment.

Table 2 shows actual case (2), example (3), and comparative example (2).
It showed durable flame retardant properties.

Example (4) A scouring and bleached cotton cloth (basis weight 250 g/m2) was immersed in the following treatment bath, squeezed with a mangle (squeezing ratio 80%), then dried at 100°C for 90 seconds, and then further dried at 150°C for 2 minutes. A drying process was performed.

Thereafter, soaping was performed at 80°C for 5 minutes in a soaping bath containing 5g/11 of a nonionic activator, and then at 100°C.
Drying was performed for 2 minutes.

Treatment bath Phenylphosphonate 180 parts Ammonium thiourea 200 parts Dimethylformamide 300 parts Water 350 parts Then, as a post-treatment, the following treatment bath was applied using a spray, followed by drying at 100°C for 90 seconds and 150°C x 2. Actual case (4) was obtained by dry heat treatment for 30 minutes.

Treatment bath Dimethylol monopropylene resin cyandiamide 120 parts water
Comparative Example (3) was 880 parts of Example (4) without any post-treatment.

Table 2 shows the durable flame retardant properties of Example (4) and Comparative Example (3).

As is clear from Table 2, it can be seen that the method of the present invention provides excellent durable flame retardant performance.

Comparative Example (4) Using the same cotton cloth as used in Example (1), it was dipped in the following treatment bath, squeezed with a mangle (squeezing ratio 70%), and then 1
Curing was performed at 50° C. for 3 minutes, and then soaping was performed at 80° C. for 5 minutes in a soaping bath containing 5 g/l of a nonionic surfactant.

Next, drying was performed at 100° C. for 2 minutes.

Treatment bath Ammonium phosphite 120 parts Dimethylol monomethyl dicyandiamide 200 parts Water
680 copies Comparative Example (5) Example (1) using the same cotton cloth as used in Example (1)
Only post-processing was performed.

Comparative Example (6) Example (2) using the same cotton cloth as used in Example (1)
I only did post-processing.

Table 3 shows Example (1), Comparative Example (4), (5), (6)
Shows the results of flame retardant performance, bending resistance, and tear strength.

Claims (1)

[Claims] 1 General formula (wherein X is -OH.-ONH4, Y is -H,
-CH3. -C2H5. ) In the flame retardant treatment of a cellulose fiber structure using a phosphorus compound shown in A flame retardant treatment method for textile structures.