DE2335749A1 - FIRE-RESISTANT TEXTILES - Google Patents

Description

The invention relates to an improved method to fiber material with an aqueous solution of tetrakis (hydroxymethyl) phosphonium salts or mixtures of these salts to be treated to give the material fire resistance properties to rent.

According to the method according to the invention, a fibrous material is obtained with an aqueous solution of a tetrakis (hydroxymethyl) phosphonium salt (hereinafter referred to as the "phosphonium salt" is referred to) or a mixture of these salts. The impregnated material is then dried and exposed to gaseous ammonia at its own pH of the solution of the phosphonium salt, being within the fiber material an insoluble polymer is formed with the phosphonium salt.

According to the invention, any fiber materials such as cotton, rayon, wool, paper, jute, ramie, wood and mixtures can be used

309886/1083

of these materials with each other and with other materials be treated. The invention is particularly effective with cellulosic textile fiber materials.

Among the suitable phosphonium salts which can be used in the present invention are the phosphates, Acetates, oxalates, other carboxylates such as lactates, glycolates, Maleates or malates and citrate salts and mixtures of these compounds.

The pH of the phosphonium salt solution is not critical and is determined by the phosphonium salt. It is not necessary, adjust the pH value of the solution.

You can impregnate the fibrous materials with the use any suitable method for aqueous phosphonium salt solutions. You can puff, spray and immerse yourself, these are common practices. The excess can, if necessary, by squeezing rollers, centrifugation or by other methods removed.

The amount of phosphonium salt applied to the textile material should be sufficient to contain between 1 to 10%, preferably between 2 and 8%, of active phosphorus, i.e. an Phosphonium phosphorus based on the weight of the textile material s.

The treated fiber material is then adjusted to a moisture content which is less than 20%, dried, the moisture content is preferably between 3 and 20%. The drying stone temperature can vary and is not critical, and the drying time is determined by the temperature and temperature used determines the weight or mass of the material. The temperature and time used for drying will be adjusted so that only the moisture is removed. That

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Drying or heating process will not "up to that." Time carried out until a fixation of the finish is achieved will.

The dried fibrous material is exposed to high concentrations of gaseous ammonia to get inside the material to form an insoluble, fire-resistant polymer. This can be accomplished by any method that allows the material to come into contact with ammonia. One can do this do by exposing the material to ammonia, by simply putting it in an enclosed space through the ammonia during the time required for the desired curing process to circulate. In the case of technical procedures it is often more practical to pass the material (as if from rollers) continuously through a chamber in which the appropriate Ammonia concentration is present. The gas temperature is usually room temperature, but it can be higher or higher be lower. The hardening, i.e. the action of the ammonia, is carried out for a time long enough to allow effect essentially complete polymerization and curing of the impregnated composition. It has been found that curing times between 1 and 60 minutes are preferred between 5 and 30 minutes are particularly suitable for the procedure with an enclosed space. The curing times depend on the amount of phosphonium salt that is on the Fiber material is deposited, and on the nature of the material itself. For the continuous ammonia treatment process typical times are generally shorter and range from about 15 seconds to 10 minutes, depending on the speed of passage through the chamber and the amount or concentration of ammonia that is in the Chamber is present or is passed through the chamber.

The treated fiber material is then washed and dried. The durability of the fire resistance of the material can be further improved by using the treated material

3 09 886/1083

■ - 4 -

rial in an aqueous solution of hydrogen peroxide according to the general teachings in Textile Chemist and Colorist, Volume 4, page 45 (1972) and J. Fire and Flammability, Volume 1, page 170 (1970), washes. In a particularly preferred method, an aqueous solution containing 5% hydrogen peroxide, based on the weight of the material, is used.

The fiber material treated according to the invention is? permanently fire-resistant, even after repeated washes. The strength and the feel of the textile materials are essential not changed by the procedure.

The method according to the invention has several advantages compared to known methods:

(1) It is not necessary to adjust the pH of the phosphonium salt solution. This means that there is no exotherm Reaction and there are no pollution problems caused by the release of formaldehyde and phosphine odor be evoked.

(2) It is not necessary to heat the impregnated fiber material at temperatures in order to produce the phosphonium salt to insolubilize and fixate on or in the fibrous material before it is treated with ammonia.

(3) It is not necessary to use highly toxic materials such as tris (hydroxymethyl) phosphine.

The following examples illustrate the invention without restricting it.

example 1

Six aqueous pad baths are prepared which contain the amounts of total phosphonium salts [tetrakis (hydroxymethyl) phosphonium phosphate / tetrakis (hydroxymethyl) phosphonium acetate Molar ratio

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nis 0.4 / 0.6] as listed in Table I are prepared. The pad baths are applied to cotton sheets using a padding process (or impregnation process). The impregnated materials containing the amounts of active phosphorus listed in Table I are dried to a moisture content of 10%. The impregnated and dried materials are exposed to concentrated ammonia for 30 minutes in a closed room. The treated material is washed with water containing 5% hydrogen peroxide, based on the weight of the material, and sufficient sodium silicate to give a pH of 10, and dried. The fire resistance of the material is determined according to the DOC FF3-71 flame test (Federal Register, Volume 36, No. 146, page 14063). A char length of 17 »8 cm (7 inches) or less corresponds to a pass of the flame test. The durability of the fire-resistant finish to washing is determined by

(1) the material in an automatic washing machine

using water at 60 ⁰ C and a synthetic detergent repeatedly washes and

(2) by determining the fire resistance according to the above test.

Baumwollbettuchstoff which has been treated by the above method, there is the DOC FF3-71-flame test after 85 home washes with water at 60 ⁰ C and a detergent. The char lengths after washing are listed in Table I.

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Table I B CD EF

% Phosphonium salts im

Bath 21.3 24.8 28.4 32.0 .35.5 "42.5

% active phosphorus

the material 3.0 3.5 4.0 4.5 5.0 6.0

Charring '

length, cm (inch) 13.7 4.57 3.8 3.05 3.56 3.81

(5.4) (1.8) (1.5) (1.2) (1.4) (1.5)

Example 2

A similar application procedure as in Example 1 was carried out to give Hemdenflanell (142 g / m = 4.2 oz./yd.) Used instead of the cotton fabric and the amount of phosphorus in%, which was deposited on the material varied. It was dried at a temperature of 107 ° C. to the specified moisture content. The dried materials were exposed to ammonia by continuously passing the material through an enclosed chamber and using a treatment time of 2 1/4 minutes. The washing and oxidation procedure described in Example 1 was then used.

The following table shows the % phosphorus deposited, the % residual moisture, and the results of the char test.

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% farewells "
ner phosphorus
owf

% Residual moisture after treatment before treatment rait NH,

Table II

Charring length. cm (inches) - DOC trial at the beginning. After 10 weeks

After 25 weeks After 50 weeks

ω
ο
ic

4.37 0.00

5.43

5.11

8.66

14.22

20.28

29.55

4.03 0.00

2.57

4.58

6.79

12.96

19.68

28.14

w α fully charred 19.3
4.8
8.6
4.6
4.8
5.3
vv

7.6
1.9

1 » ⁸
1.9
2.1

VV-VV

4.8-3.8 4.0-7.6 8.1-4.1 4.1-4.6 19.8-4.1

15.25 (6.0) w-vv

vv 13.3-4.3

5.1 2.0) 5.1-4.8

11.4 4.5) 4.3-3.8 5.8 2.3) 4.1-4.3 3.8 1.5 w-21.0

16.5 6.5) 16.7-vv (

1.9-1.5 1.6-3.0 3.2-1.6 1.6-1.8 7.8-1.6

W-W

VJl , 2-1.7 2 , 0-1.9 1 , 7-1.5 1 , 6-1.7 w-8.3) 6-vv)

VV-W

3.5-4.8 3.5-4.8 8.6-4.0 6.4-4.3 12.2-4.6

1.4-1.9 1.4-1.9 3.4-1.6

2.5-1.7 4.8-1.8

6.6-4.1 (2.6-1.6)

4.8-5.8

6.3-7.9

3.8-4.6

11.6-4.3

1.9-2.3 1.7-3.1 1.5-1.8 4.6-1 ,?

W-W

7.6-4.6 (3.0-1.8) 19.3-12.7 (7.6-5 4.1-8.1 (1.6-3.2) 4.6-4 , 6

,, (, 3,) ,, 11.9-4.8 (4.7-1.9) 6.6-5.1 10.9-12.4 (4.3-4.9) 6.6-6, 6 8.4-9.7 (3.3-3.8) 8.6-4.3

2.6-2, ui

2.0-2.0

3.4-1.7)

VV-VV

23357 ^ 9

The figures given in the table above show the unsatisfactory fire resistance properties, the shirt flannel possesses if the material has insufficient moisture or too high a moisture content Moisture content is dried.

Example 3

The procedure of Example 2 is repeated using the amount of material used to obtain a deposition of about 6 _f k% phosphorus on the Hemdenflanell. The remaining moisture content is varied. In this example, the treatment time for continuous treatment in the chamber with ammonia is 10 minutes. The results are shown in the table below.

% remaining Char length, cm (inches) - DOC test

Humid At the start After 10 After 25 After 50 salary Weeks Weeks Weeks 0.00. - W. —__ ___ 8.08 4.3 (1.7) 4.8 (1.9) 4.3 (1.7) 4.3 (1.7) 9.07 5.1 (2.0) 4.6 (1.8) 4.8 (1.9) 4.6 (1.8) 12.02 3.6 (1.4) 5.8 (2.3) 4.6 (1.8) 3.8 (1.5) 13.33 5.1 (2.0) 4.8 (1.9) 5.1 (2.0) 4.6 (1.8) 20.13 6.9 (2.7) 4.6 (1.8) 4.1 (1.6) 4.8 (1.9) B e i s ρ i el 4

The procedure of Example 2 was repeated using sufficient refractory to obtain a percent phosphorus deposit of from about 4.75 to about 4.9. The materials were dried to different residual moisture contents at 107 ° C and the treatment time with ammonia in the continuous curing process was also varied.

3 09886/1083

Tabel

Continuous % Remaining Hardening process 6th , 7 10 , cm (5.1) (inches) - DOC test (4.0) 2.9 50 1 , 9 , 6 , 3 ,8th 1 Cook 9) Treat Damp Char length 1 , 6 Weeks 2.4 25 weeks 2.0 ^J , 6 , 6 J ,1 8th 8th) lung activity To Be 2 , 5 (2.1) 2.1 1.9 ,8th ,8th , 4 ,8th 1 9) Time start 3 , 9 W. 1.5 1.6. W. , 3 , 3 , 6 3 (Min.) 2.83 W. 7.6 10.1 1.6 1.9 W. VV , 5 "8th 1 0.63 4.51 W. 4th ,1 12th 1.5 W. 3.8 4.0 W. 3 5 W. W. 4th 7.24 W. , 5 6th , 9 1.6 5.3 1.8 VV 3 5 3 6, P ' 4th 12.22 17.0 2 ,1 5 ,1 2.1 3.8 1.9 9 4th 8th 5 3, (1, 9 19.03 4.1 4th ,8th W. , 3 2.0 4.0 3.4 9 4th 4th 5 5, 7th 28.55 6.4 6th , 9 19th 2.0 9.6 1.6 4th 4th 8th 5, 4.93 9.9 3 , 3 5.9 W. 2.5 4th 4, 1, 1.25 6.83 W. ¹ -2 , 0 4th ,8th 2.4 4.3 (1.7) 1, 9.72 10.4 ρ , 6 5 ,1 1.7 3.6 1.4 1, 14.19 3.8 2 ,1 5 , 3 5.2 3.6 1.4 1, 21.23 5.3 ,1 5 ,1 1.4 5.10 (2.0) 1 30.18 - 12.2 • 7 , 5 14th ,1 2.2 11.2 (4.4) 2, 0 4.27 17.5 Λ ,8th 6th , 9 1.1 7.4 2 3 2.50 5.20 VV Λ , 5 4th ,1 2.0 5.1 . ^, 7th 10.12 7.6 1 ,1 13th , 3 1.7 4.8 8th 13.81 6.6 1 , 9 3 , 2 2.0 4.1 20.77 5.3 1 ,8th 5 , 6 4.9 4.8 28.90 5.3 2 , 6 1.9 10.2 7, -52 8.9 1 , 2 5 ,8th 1.5 4.6 * - » 5.00 9.65 4.6 2 , 5 4th ,1 1.3 "4.8 1.6 14.48 3.8 1 ,8th 5 , 3 1.8 8.6 2.0 .5, 18.44 2.8 1 , 3 12th ,1 1.6 4.1 1.7 5 22.47 4.8 2 ,8th 4th , 4 1.7 6.3 2.0 0 38.93 4.6 3 ,8th W. 2.0 2, 3 7.07 W. 3 ,8th 4.1 1, 4th 10.00 9.69 3.0 4th , 3 5.1 2, Q 14.32 6.3 4th , 6 4.3 2, 17.37 4.6 4th ,1 5.1 1, 21.71 3.3 , 3 5.1 P i e 1 7.1 By S 4th 5 0 1 6th

The application procedure described in Example 2 was repeated, applying four different fire retardant compositions to shirt flannel and using the phosphate acetate combination as in Example 1 and separately using the tetrakis (hydroxymethyl) phosphonium acetate, phosphate and oxalate salts. The following table shows the amount of phosphorus deposited on the material in % t the remaining moisture in % and the charring lengths.

309886/108 3

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309886/1083

Claims (5)

- 11 claims 1. Improved process of making fibrous textile materials to equip flame retardant, in which the following stages are carried out (A) impregnating the textile material with an aqueous solution of tetrakis (hydroxymethyl) phosphonium salt or Mixtures thereof, (b) drying the impregnated textile material at an elevated temperature, and (c) treating the impregnated and dried textile material with gaseous ammonia, characterized in that step (a) is carried out at the own pH of the solution of the phosphonium salt. 2. The method according to claim 1, characterized in that the material is so strongly impregnated that on the material from 2 to 8% of active phosphorus can be deposited. 3. Method according to claim 1 and 2, characterized in that that the material is dried to a moisture content between 3 and 20%. 4. The method according to any one of the preceding claims, characterized in that the ammonia treatment batchwise or is carried out continuously. 5. The method according to claim 1, characterized in that the phosphonium salts used are phosphates, acetates, oxalates, Lactates, glycolates, malates or citrates are used. 309886/1083