DE2028999A1 - Process for making cellulose textiles flame resistant - Google Patents

Description

Chemical factory Pfersee lo.6.197o

GmbH _Λ

Patent application

Process for making cellulosic

textiles

Additional registration to P 19 06 389.9

In the main patent (German application P 19 06 389.9)

is a process for making materials flame-retardant that are wholly or partially natural and / or regenerated Cellulose fibers exist, protected, which is characterized in that these materials with aqueous liquors, which trisaziridinylphosphine oxide, cyanamide and at least one Ammonium salt of phosphoric, amidosulphonic, sulfuric or nitric acid contained, soaked, dried and, if necessary, then condensed at an elevated temperature.

It has now been found that instead of APO (Trisaziridinyl phosphine oxide) in the same way compounds of the formulas

_{3a
(- <} 0Η ₂ (I)

^0H 2> b

(a = 0, l-2.6; b = O.3-2; C = O-I; a + b + c = 3)

(-NH-CH-V
and / or ClCH ₂ -P (O) ^ ^a (II)

ν ^CH 2> b
(a = 1, 0-1, 8 and bsO, 2-1.0; a + b = 2),

where the indices mean values of the methylamido, Ätliylenimido- and indicate amido groups, can use. These compounds are known, for example, from the Netherlands Disclosure Office 68 09 569 bsw. the Swiss sponsor 481 257

10 9 8 51/17 9 3 ^{0 RiGWAL} ^ ^{? £ CTED}

• c—

It was surprising to find the wash resistance of an Elammfest finish with these compounds in the same way, the combination with cyanamide and ammonium salts you phosphorus-j Amidoaulfonic, sulfuric and / or nitric acid can improve. The method according to the invention makes it possible to achieve a substantial degree smaller amounts of substituted aziridinylphosphine oxides of formulas I and II excellent quick-release flame-retardant effects than when these substituted aziridinylphosphine oxides are used alone. It's surprising that the effects according to the invention can only be achieved if cyanamide is present in the equipment fleet, while by replacing the oyanamid with similar compounds, such as For example, dicyandiamide, guanidine or guanidine salts, the "washing resistance of the flame-retardant effects is reduced quite significantly will.

The amount of the compounds I and / or II required to achieve wash-resistant flame-retardant effects depends on the one hand on the plotter absorption and the weight of the odorous material and on the other hand on the desired wash-resistance of the flame-retardant effects. The amounts of compounds of the formulas I and / or II preferably used per liter of finishing liquor are between approx. 60 and 80 #, 150 to 300 g, in particular 150-260 g, for a liquor pick-up of the textile material. The amount of ammonium salts should be greater than $ 2 based on the amount of compounds of the formulas I "and / or II used. The amount of cyanamide must be more than $ 1 based on the finishing liquor, in particular more than $ 2.5 The upper limit for the concentration of cyanamide is not critical. Excellent effects are also achieved with 10 fi . The ammonium salts of phosphoric acid and / or sulfamic acid are preferably used »

About the stability? To ensure the equipment liquor, it should have a pH value between 5.5 and 8.5, in particular 7 to 8, with these pH values around 7 di @ stability of the equipment liquor even over several periods at indoor temperature guaranteed 1st. At pH values of the liquor that is below or are above the specified limit, preferably, occur

109 8 51/1793 original inspected -3-

207R999

hydrolytic cleavage or further condensation, which leads to a substantial reduction in the stability of the liquor and this can lead to a reduction in the flame-retardant effect. The liquor pH can be adjusted by customary means, in particular however, by ammonia or the corresponding acids Getting corrected.

All or some of them can be used as cellulose materials Cellulose fiber, existing materials, but especially ! Textiles which consist entirely or predominantly of cellulose fibers can be considered. .

Example 1;

A section of cotton poplin weighing 126 g was with a liquor containing 50 g of cyanamide, 50 g of diammonophosphate and 250 g of a compound of the formula

(~ NHCH ₃ )

(eel, 3; b = l, 7 and c ^ O)

contains, soaked, squeezed off to a liquor pick-up of approx. 70 ^, ^{dried at HO 0} G and ^{condensed at 160 0} C for 5 minutes. When tested for flame resistance, Bas fabric shows a burning time of 0 seconds and an afterglow time of 0 seconds even after 20 boil washes.

In this as well as in all of the following examples, the boil washes were carried out in a commercially available, program-controlled manner Household washing machine carried out. With normal, non-softened water in a liquor ratio of 1:15 using 2 g / l of a common household detergent washed.

The washing program was as follows:

No pre-wash

Main wash: 47 minutes including heating to 95 °

1st rinse cycle: 2 minutes including drain

(each with

cold water) 10 9 8 51/17 9 3 ORIGINAL IHSPEGTED

2nd rinse cycle: 2 minutes with running water

Spin for 1 minute

3rd rinse: 3 minutes with running water

Extract 3 minutes

It is dried hanging at room temperature.

The test for flame resistance is carried out in accordance with BIN 53 906. According to this DIN rule, the 75 x 150 mm sample is measured a hanging bracket attached so that its lower narrow edge is flush with the two parallel ends of the Hanging bracket completes. The bracket is then hung in the firing box ^. The firing box must be set up completely draft-free. If it is installed in a fume cupboard, its ventilation must be shut off during the experiment. The burner flame is with With the help of the visor plate adjusted to a height of 40 mm ± 1 mm, the combustion chamber door closed and the burner under the center the lower edge of the sample so that it hangs 20 mm into the burner flame. At the moment of pushing the burner flame starts the stopwatch. After expiration The burner is withdrawn about 100 mm during the test.

Burn boxes are placed during the sample change after each test and ventilate the fume cupboard for at least 2 minutes.

The duration of the test depends on the weight per unit area and amounts for basis weights between 300 - 500 g / m 10 seconds or at 200-300 g / m 8 seconds. The sample will burn after removal If the burner continues, the burning times are measured until the last glowing spark is extinguished.

For comparison, sections of the cotton fabric specified above were finished in the same way with the following liquors:

a) 50 g / l diammonophosphate 250 g / l compound I ¹

b) .100 g / l diammonophosphate ORIGINAL INSPECTED

250 g / l compound I ¹

c) 150 g / l diaamon phosphate

250 g / l Compound I · 109851/1793

The samples finished in this way became after 5 × 10, 15 and 20 boil washes tested for their flame resistance. The results are in Table I below with the results of the invention Equipment summarized.

fleet

Flame resistance after χ boiled washes

10

15th

20th

50 g / l cyanamide 50 g / l diammonophosphate 25o g / l compound I *

according to the invention

0/0

0/0

0/0

la 50 g / l diammonophosphate 250 g / l compound I ¹

Comparative experiment

burns

burns burns

b 100 g / l diammonophosphate 250 g / l compound I ¹

Comparative experiment

burns

burns burns

c 150 g / l diammonophosphate 250 g / l compound I ¹

Comparative experiment

burns

burns burns

In the results of the flame resistance, the means first digit the afterburn time in seconds, the second digit the afterglow time in seconds.

Example 2:

A green cotton atlas (square meter weight 300 g) was soaked in a liquor containing 50 g of cyanamide, 70 g of diammonophosphate and 210 g of a compound I "(a = 2, b = 1, c = 0) per liter a pick-up of approximately 75 # squeezed out, dried at 110 ⁰ C and condensed for 6 minutes at 150 ⁰ C. the fabric shows at the flameproof test even after 20 washes cooking a fuel and afterglow time of 0 seconds.

10 9 8 51/17 9 3

ORSGINAL. -

-5-

■ -6- 2C./a ^:) 99

Example 3:

A white cotton atlas (square meter weight 300 g) was impregnated with a treatment solution containing 30 g of cyanamide, 50 g of biammon phosphate and 255 g of a compound II ¹ (a - 1.0, b = 1.0) per liter a liquor pick-up of approx. 65 ί> squeezed off, dried at 100 ° C. and condensed at 165 ° C. for 5 minutes. When tested for flame resistance, the fabric treated in this way shows a burning time of 0 seconds and also an afterglow time of 0 seconds even after 20 boil washes.

Example 4:

A blue cotton twill (m2 weight 220 g) was made with a liquor containing 30 g of ammonium sulfamate, 70 g of cyanamide and 250 g of a compound I ¹¹¹ (a = 1.5, b = 1.3, c = 0.2 ) contains, soaked, squeezed off to a liquor pick-up of 80 I> ^{, dried at HO 0} C and ^{condensed at 160 0} C for 5 minutes. Even after 15 washes, this fabric shows a burning and smoldering time of 0 seconds.

Example 5;

A white Sellwollrenforco (square meter weight 180 g) was made with a liquor containing 50 g of cyanamide, 50 g of diammonophosphate and 230 g of the compound i ·· «(a = 1.8, b = 1.2, c = contains 0), impregnated, squeezed off to a liquor pickup of 100 #, dried at about 100 ⁰ C and condensed for 5 minutes at 170 ° C. The fabric is after 10 washings cooking a fuel and Machglimmzeit of 0 seconds "

ORIGINAL INSPECTED

109851/1793

Claims (3)

^ 202B999 claims 1.) Process for the flame retardancy of materials that wholly or partially from natural and / or regenerated Cellulose fiber! exist, according to DBP (German Registration P 19 06 389.9) »characterized» that instead of trisaziridinylphosphine oxide, compounds of the formulas (-! ßiCH ₃ ) _a (a5sQ _f l-2.6; b = 0.3-2; C = OI; a + b + c «3) and / or ClCH ₀ -P (O) J " _n ^{3 a} (II) (a = l, 0-l, 8 and bsrO, 2-1.0; a + bas2) be used. 2.) The method according to claim 1, characterized in that the aqueous liquors with a liquor uptake of 60 - 80 ^ 150 - 300 g / l of compounds I and / or II, at least 10 g / l of cyanamide and at least 20 g / l of one Contain ammonium saltsβ of phosphoric, amidosulphonic, sulfuric or nitric acid. 3.) Method according to claim 1 and 2, characterized in that that the pH of the aqueous liquor is between 5 _f 5 and 8.5, in particular 7 and 8. 4.) Process according to Claims 1 to 3, characterized in that the ammonium salts used are diammonophosphate and / or Ammonium sulfamate can be used. 109851/1793