DE1285442B - Process for flame retardant finishing of cellulose textiles - Google Patents

Description

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There are numerous methods of flame retardancy - great rigidity and the associated low rigidity

prepare cellulosic textiles using tear and tensile strength, thereby overcoming that

Aminoplast-Phosphorus-Condensates (Methylol-Phos- man of condensation by heat treatment a

phorpolymeren) known, which can follow partial hydrolysis with mineral acids in the condensate molecule. Contain nitrogen atoms. These condensates have not only significant amounts of acid

excellent fire retardant properties. It's used up, but it also needs to be neutralized

however, it is not enough to equip the textile material with a flame-retardant finish.

but it should still be used even after repeated washing. From British patent specification 882 993 it is

its fire-retardant properties and at the same time knows that an aqueous immersion

the desired grip, the durability, the use of tear-off impregnation solution, the THPC, urea

Maintain strength and tensile strength. Of the kind and contains methylolmelamine. The impregnated

and the way in which the aminoplast-phosphorus condensates textile is dried for a few minutes at 90 ° C,

after application to cellulosic material, how and then the co-condensable

Cellulose textiles, which are hardened, hang in components through treatment with concentrated

to a considerable extent these properties of the treated 15 aqueous ammonia solution hardened.

Product. After all, it's from the UK patent specification

If you know the aminoplast-phosphorus condensates 9O6 314, cellulose textiles are flame-resistant as a result after applying it to cellulose textiles in the equip that it is with an aqueous solution Heat cures, is often the tear strength and / or dispersion of a precondensate from THPC, Reduced tensile strength of the fabric. If the heat 20 impregnates urea or methylol melamine, dry cure is not carefully controlled, a net and with aqueous or gaseous ammonia takes place uneven hardening of the condensates, and often treated. Again, the difficulties that if the condensate inside the fabric still occurs during the ammonia hardening process, this cannot be avoided, considerably soluble in water. The durability of the flame- Another difficulty encountered with heat curing solid finishing of such products is generally impaired for the manufacture of flame-retardant cellulose goods, and often the cellulosic material occurs, is that this process is often only stiff and / or boardy and therefore does not have to be carried out on yard goods in the weaving mill desired properties. can and does not opt for ready-made articles in one

From US Pat. No. 2 911 322 it is known that conventional laundry is suitable. In many cases it can the aminoplast-phosphorus condensates will not be disadvantageous in the 30, since it is the application of flame-heat, but to harden with ammonia. On this repellent finish on new clothing In the same way, the heat-hardening of the goods made by the meter is limited, the previously flame-resistant from condensates Any difficulties that occurred were overcome and armed. Furthermore it can with such ver-this However, the procedure is not completely impossible to drive again Satisfactory, as treat with ammonia 35 during the hardening process, which was previously made flame-proof, the condensate is still soluble in ammonia and is made to renew its flame-resistant properties, the tissue is leached out. Once that is out- accordingly, procedures for flame-proofing are resolved Condensate is desired by the ammonia in the insoluble finish of cellulose goods, both of which borrowed condition is transferred, it is on the upper yard goods in the weaving mill as well as in laundries surface of the material can be carried out in the form of white spots 4 ° ready-made articles, redeposited, which gives the textile a bad appearance. The present invention reduces the pre-appearance to lend. overcome the difficulties and disadvantages mentioned.

In the process of US Pat. No. 2,993,746, the invention relates to a process for Cellulose textiles with an aqueous impregnation and flame retardant treatment of cellulose textiles by dissolving them, the tetra- (hydroxymethyl) -phosphoniumchlo- 45 impregnate with a tetra- (hydroxyorgano) -ride (THPC), methylolmelamine (aminoplast former), phosphonium halide, a water-soluble, cycein mixed-condensable carbamic acid derivative and borrowed, mixed-condensable aminoplast formers contains a catalyst (triethanolamine), a flame-resistant, mixed-condensable carbamic acid derivative and a equipped by the impregnated textile material after bath stabilizer containing aqueous solution, dry Drying a heat treatment and then attaching the impregnated cellulose textile material by heat-sealing a partial hydrolysis through strong treatment and hardening of the mineral acids on the cellulose textile is subjected. The textile material is well applied substance mixture with ammonia, then with a sodium carbonate solution, compounds or solutions delivering new ammonia neutralized and then dried. "of amino compounds that have at least two reactive

If animoplast phosphorus condensates contain ionic hydrogen atoms in the molecule after 55, the application to cellulose textiles by heat, which is characterized in that as a bath stabilizer treatment hardens, the tear and tensile strength in the aqueous solution becomes alkali or alkaline earth strength of the tissue is considerably reduced. The hydroxide, carbonate or bicarbonate is used Cellulosic material becomes stiff, and the durability of and, before curing, the impregnated cellulosic flame resistance is relatively low. A wide range of textile goods both dried by heat treatment and Another disadvantage of this process is that the substance mixture applied also precondenses the thermosetting is not siert in the desired manner until the constituents of the aqueous solution can be controlled, so that the curing takes place unevenly in an aqueous ammonia solution insoluble pro. It therefore remains inside the fabric after the duct has passed.

Heat treatment of the condensate is often still water- 65 In practice, the method of the invention is so

soluble. carried out that the cellulose fabric initially

According to US Pat. No. 2,993,746, an attempt was made to impregnate the solution with a) the tetra - («- hy-

one the above-mentioned disadvantages, especially the droxyorgano) phosphonium halide, b) the water

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soluble cyclic, mixed-condensable amino xymethylcyclohexyO-phosphonium chloride ^ etra- ^ x-hy-

plasticizer, c) the mixed-condensable carbamine- droxypropionyl) - phosphonium chloride, tetra- (x-hy-

acid deriyat, including here urea, thiourea, hydroxybutyl) phosphonium chloride or their compounds

Mix biuret, ethylene urea or dicyandiamide. The phosphonium compounds can be found in

will stand, and d) the aforementioned inorganic 5 monomeric or partially polymerized form

Contains bath stabilizer. The impregnated will then be used as long as they are still water-soluble.

Cellulose fabric heated until the mixed condensable For example, one can Tetrahydroxymethylphos-

Components partially combined to form a product phonium chloride, the preferred phosphonium compound

have reacted, the bond in ammonia, heat and partially polymerize before

solutions is insoluble. Then you treat it with io you dissolve it in water.

Cellulose textiles impregnated with the precondensate as water-soluble, cyclic, mixed-condensable Ammonia, until the precondensate is completely out of the aminoplast formers, the triazines and the cychardened and is insoluble in water. That after the loss of dimethylolalkylene ureas in question. Ty driving Cellulose fabrics treated according to the invention are typical examples of suitable triazines are the methyl permanent Flame-resistant, even after repeated olmelamines, such as the mono-, di- and trimethylol holtem Wash, and shows no signs of melamine, modified methylolmelamine, like the one Condensate stains on the surface as a result of a trimethyl ether of trimethylolmelamine, triazone, partial dissolution of the impregnation compound during such as dimethyloltriazon, or their mixtures. Typical the ammonia hardening. In addition, the handle is exemplary of suitable dimethylolalkylene cyclic fabrics Dimethylolethyleneurea or Divon are essentially unchanged from ureas untreated fabric, and the tear strength methylolpropyleneurea. Is trimethylol melamine and consistency are comparable to untreated the preferred aminoplast former, and out of this Tissue. This connection will be the main reason below

It was found that the use of the mentioned.

organic bath stabilizer in the form of an alkali 25 As already mentioned, urea, biuret, ethylene urea or dicyandiamide are obtained as carbamic acid derivatives in the process according to the invention or alkaline earth metal hydroxide, carbonate or bicarbonate. Namely, so far have been used as stabilizers for. Of these, urea and thio are preferred for this purpose, acidic or acid-forming stabilizers, urea. By adding these compounds such as triethanolamine, used. Presumably causing fertilization, the amount of expensive in any way the stabilizer used in the process of the invention tetra- (- -hydroxyorgano) -phosphonium halide can be delayed or inhibited. Since urea and thiourea are preferred during the condensation of the mixed-condensable processes according to the invention, components of the impregnation bath are specifically mentioned below during the
exhibit heat curing. The impregnation bath therefore remains. The preferred bath stabilizers are sodium over a longer period of time and, at higher temperatures, in hydroxide, sodium carbonate and sodium bicarbonate. usable condition. This reduces the frequency of a particularly preferred impregnation bath for replacing the bath, and the method according to the invention contains the following evidence.
Deposits during chemical hardening, which turn out to be 4 °
showing white spots avoided. After all, the tetrahydroxymethylphosphorus is

Methods of the invention equally useful phonium chloride 23 to 32 percent by weight

both for yard goods in the weaving mill and for _XT . _{,,, n} . ,. _n , ... ,

Confections using conventional sodium hydroxide 0.4 to 0.6 equivalents

Laundry facilities. 45 ^base ^ ^Mo1 phosphonium

The Im-cnlond used in the process of the invention

impregnation solution contains the aforementioned components trimethylolmelamine 6 to 9 percent by weight

preferably in the following proportions: urea 4 to 7 percent by weight

Tetra - («- hydroxyorgano) - ₅₀ water 48 to 65 percent by weight

phosphonium halide 10 to 40 percent by weight

Water-soluble, cyclic In addition, the impregnation bath can have other

Contain co-condensable ingredients, such as tissue lubricants

Aminoplast formers 5 to 15 percent by weight and wetting agents. If the latter connections

Carbamic acid ... 1 to 10 weight percent ⁵⁵ fertilize the impregnation bath are added, are

they generally in amounts up to about 3 weight stabilizer 0.25 to 0.75 equivalent percent.

Base per mole of phosphoni- During the preparation of the impregnation bath, the

Reconnect non-aqueous components to water preferably

Water 35 to 80 percent by weight ^{6o added} in the order given above.

In general, it is advisable to stir the bath

Typical examples of suitable tetra- («- hydroxy- so that the non-aqueous components are as full as possible

organo) phosphonium halides are tetrahydroxy- constantly dissolved in water. As soon as the im-

methylphosphoniumchlori ^ Tetrahydroxymethylphos- impregnation bath has been prepared, it is preferred

phonium bromide, Tetrahydroxyäthylphosphoniumchlo- 65 wise to a temperature below about 29 ⁰ C a

rid, tetra- (x -hydroxypropyl) -phosphonium chloride, made to ensure the maximum stability and usability

Tetra - (& - hydroxyallyl) phosphonium chloride, Tetra («- ability of the bath to be maintained. Typical working tem-

hydroxybenzyl) phosphonium chloride, tetra- (x-hydro- temperatures for the impregnation bath are around 18 to

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about 29 ^° C. Of course, the bath can also have higher or lower temperatures used when the amount of condensate taken up is desired.

However, temperatures can be considerably higher. When using conventional washing machines

half about 29 ° C the lifespan of the bath, which is essential for the impregnation of cellulose textiles, should in general reduce. Furthermore, during periods of heat, the amount of impregnation absorbed may be appropriate be to cool the impregnation bath. In solution in objects within an area these cases you can z. B. about 15 to about 25% of about 65 to about 85 percent by weight, so that Replace the water in the impregnation bath with ice to give the finished product a condensate content in the area keeping the bath temperature in the desired range, from about 16 to about 22 percent by weight, without the concentration of the aqueous solution of the sub- ίο The amount is preferably absorbed To influence the punch mix unfavorably. Impregnation solution in the impregnated articles

Once the impregnation bath has been adjusted to the above about 70 to about 75 percent by weight, so that the The amount of condensate absorbed can be estimated to be about 19 to Solution on cellulosic textile goods in any suitable 21 percent by weight. In the case of cellulose textiles that Manner. In general, the type of suspension that is treated in the weaving mill is the preferred one How the impregnation solution is applied to the textile Amount of impregnation solution absorbed in the Bevon its shape. As mentioned earlier, the range can range from about 60 to about 80 percent by weight aqueous solution of the substance mixture both to a condensate content in the range from about 18 to Sold by the meter as well as ready-made articles to yield around 24 percent by weight. In particular will. When processing yard goods, the amount of impregnation solution absorbed is in the 20 Weaving mill can use the impregnation solution in a block in the range of about 70 to about 75 percent by weight, hütte and the cellulose textiles by mixing the absorbed amount of condensate in the lower in the solution to be treated. Thereafter, the range will be from about 19 to about 21 percent by weight, As soon as the cellulose textile material is impregnated and the

Suitable devices are carried out to separate excess amounts of the impregnating solution taken up on the solution. When the impregnation is set to the desired value, the material, ready-to-wear articles such as shirts, nightgowns or long enough to allow the workwear to condense, the process according to the invention can partially condense mixed-condensable components in conventional washing machines. In this case, the impregnating solution will be essentially insoluble in a solution containing ammonia. These pre-suitable containers are set up, and then the condensation is generally carried out in such a way that the goods to be treated come into contact with the solution in such a way that aldehyde groups are brought into contact during the mixing. This can take place in any suitable way, condensation occurs, no reaction with the cellulose molecules of the material to be treated, for example by dipping the goods into the solution, or moistening them in a washing drum or in impregnated in an extractor. To the extent that the condensation product in my case is essentially preferred, the last-mentioned impregnation method is ammonia-containing solutions, since in this case the loss of impregnation solution is insoluble. Preferably temperatures are kept to a minimum. about 93 to about 160 ⁰ C and curing times of about

An important factor in the inventive method 40 used for 0.5 minutes to about 1 hour. When driving long is the amount of treated cellulose- rer curing time will be at lower temperatures substance mixture absorbed by the material. Naturally worked.

Too low an amount of the absorbed can be borrowed. The partial thermosetting described above

Mixtures of substances result in a condensate that can be contained in the impregnated cellulose material in any has poor flame-retardant properties, and / or suitable device can be carried out, and a condensate, in which the durability of the flame - either such as it is pre-solidified in the weaving mill are reduced after repeated washing or as they are in normal laundries. It was also found that too high a turn should be. For example, you can use the partial Absorption of condensate can result in a product, heat curing in a loop dryer, in one which has an unsatisfactory grip, d. H. a 50 conventional drum dryer, in a tumble product, that is stiff and / or boardy. Generally a dryer or similar device found that amounts of ingested result. In some cases it may also be desirable Mixture of substances in the range from about 16 to about the impregnated cellulose material of a drying Weight percent of the treated material to be subjected to freezing, either before or at the same time as the deliver great results. 55 partial heat curing. If drying before

Since the absorbed amount of condensate is carried out during the partial heat curing, one draws Finally, fire-retardant cellulose is generally obtained, the drying conditions so material is to a considerable extent dependent on the adjust that a moisture content in the dry amount of the mixed condensable material taken up is obtained from about 5 to about 10%. on The impregnation solution during the impregnation process, there is practically no hardening of the that the control of the absorbed impregnation compound during drying, so that the Amount of impregnation solution during the impregnation degree of hardening better in a separate heat setting an important factor is whether the impregnation hardening stage can now be controlled. With equation In the weaving mill or a laundry, drying and heat are carried out continuously will. It has been found that in general curing is generally preferred to this an absorption of impregnation solution in the area of operation at low temperature and long about 65 to about 100 percent by weight of the reaction times to be treated, generally within the prescribed range Good gives a finished product that the named area to carry out. When confection

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cellulose-based items are impregnated, the chemical hardening can be continuous

and the procedure should be carried out in a washing machine. If, however, the finished treatment

is carried out, the partial heating of the treated fabric is carried out in one wash

Generally intended to include curing at slightly lower tempe- ratures, jiggers can use chemical curing than drying in the weaving mill. 5 more useful in a jigger in the first section

When using a pelvic dryer to be carried out partially. An example of a special

Heat curing of the applied mixed-condensable solution of the curing mixture contained in such

Mixture of substances are drying temperatures weaving device can be used is

in the range from about 93 to about 121 ⁰ C and dry the following:

Operating times in the range from about 20 to 60 minutes io w _ater 3801

preferred. When performing the partial heat- AmmoniümsulVai '[VY'.'.'.'.'.'.'.'.'.'.'.'.'.'.'. 22.7 kg

hardening m weaving, z. B. my conventional sodium carbonate 13.6 kg

Drum dryers, the preferred hardening sodium bicarbonate is 22.7 kg

temperatures in the range of about 132 to about 160 C.

and curing times between about 1 and about 15 after impregnating the fabric with it

5 minutes. Solution of the hardening mixture is generally

As soon as the impregnated cellulose material partially requires a dwell time of about one minute,

heat cured and the desired partial condensation before the subsequent processing operations, such as

sation of the mass in the material has taken place, the washing will be carried out,
acted cellulose material a chemical hardening ao In the chemical hardening of impregnated

With the help of an ammonia-supplying compound, the ready-made articles in a washing machine can

subject. For chemical hardening, ammo-chemical hardening can expediently take place in the washing drum

niakgas, aqueous ammonia, including Ammo can be carried out. This is the first cycle

nium hydroxide, solutions of amino compounds, the post-washing process in the hardening stage. at

The at least two reactive hydrogen atoms 25 this process becomes a hardening solution from 3801

contained in the molecule, such as amines with a primary water with 7.571 28% ammonia in the washing

Amino group, hydrazine or alkyl-substituted hydro-drum, and the cellulose fabric is in

drazine, ammonium carbonate or other lightly agitated this solution for about 3 minutes. One can also

dissociable salts of weak acids with ammonia, a solution of the hardening mixture similar to how

such as ammonium acetate or ammonium formate, they are sold in the weaving device described above

be turned. In addition, chemical hardening can be used to add to the washing drum

processing of the impregnated cellulose material with such a solution can contain the following ingredients

an aqueous solution containing the following amounts:

Mixture of the ammonium salt of a strong acid, water 3801

such as ammonium sulfate, with an alkali carbonate and 35 ammonium sulfate 11 3 kg

an alkali carbonate such as sodium carbonate and sodium bicarbonate 68kg

Sodium bicarbonate contains sodium carbonate . ^ [Y. '.'. '.'. '.'. '.'. '.'. '.'. lUkg

For the sake of simplicity, it is generally preferred

before, the chemical hardening of the applied mix- The treated cellulosic material is in the

condensable, precondensed substance mixture given 4 ° washing drum, which contains this solution,

with an aqueous »solution of ammonia, such as Ammo and the drum is moved for about 1 minute,

nium hydroxide, or the aforementioned aqueous In general, the concentration of the ammonia

Solution of the mixture of ammonium sulfate, sodium hardening solution, which is used in a washing machine

to perform carbonate and sodium bicarbonate. will be lower than in a weaving mill

The chemical hardening is carried out as long as 45 direction. The reason for this is that in the washing

until the impregnation compound is practically completely machined a more complete saturation of the cellulose

hardens and thus the mass in the full cellulose material is achieved with the ammonia hardening solution

is constantly converted into the water-insoluble state than in the weaving device. Accordingly

is. Of course, the ammonia content of the hardening solution fluctuates better than the chemical one

Curing time required and it depends on the 50 used, and therefore can be lower

Amount of absorbed condensate is applied to the ammonia concentrations in the solution

To be treated as well as the type of cellulose.

materials, hardening times of about 1 to about After the chemical hardening of the cellulose material

5 minutes is typical. Similarly, it can also be obtained by washing non-condensed rials

the ammonia substances and the like used for chemical hardening are freed.

concentration fluctuate, but result in amounts of

about 3 to about 10 weight percent in a satisfactory conventional manner, e.g. B. in a rope washer, in one

Results. endless, open washer or a jigger

Just like the impregnation and the partial leads. The washing can expediently z. B. with a Heat curing, chemical curing can be carried out using either 60 aqueous soaking solution in devices that are available in the weaving mill, small amounts of sodium carbonate and perborate or in conventional washing machines depending on how long it lasts. When using a washing machine, this will Type of cellulose textile goods to be treated by washing in the washing drum immediately after be guided. In the treatment of yard goods, chemical hardening is carried out. In both cases Chemical hardening can be carried out in a padder or 65 preferably followed by drying after the washing process a jigger using the foregoing in a conventional manner. Then the material can Hardening mass are carried out. When the normal finishing process, such as non-shrink padding in series with the thermosetting furnace, or subjected to calendering.

809648/1900

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The cellulose textile material treated by the process according to the invention is even after numerous ",. .. ". _T ..,. , “Permanently flame-resistant washing processes. Besides- ^Es ^ ^{0 ei} f ^wa _t ^ß "S ^{e Losun} S ^ Sender In addition, this material has produced a practically unchanged composition:

Tensile strength, tear resistance and unchanged handle. 5 ^{ewic sprozen}

Furthermore, the treated cellulose textile material is in tetrahydroxymethylphosphonium chloride,

In contrast to the 80% aqueous solution 27.3 treated according to known processes

Delten material that only chemically cures Trimethylolmelamine 7.3

was subjected to resin free from urea 4.5

on its surface. io sodium carbonate 4.2

The inventive method is in the case of water 56.7

play further explained. Quantities relate to

on percent by weight, unless otherwise stated, cotton cloth is immersed in this solution

is. The flame-retardant properties were and then squeezed out until the moisture absorption

according to the method of the American Association of 15 would take 100%. The impregnated cotton

Textile Chemists and Colorists, test standard AATCC- cloth is dried for 1 minute at 121 ° C and 1 minute

Base 34-1952, the tensile strengths according to the test standard heated to 137 ° C. Then the cotton cloth

CCCT-1916, 5100, and the shrinkage after being divided into four samples and then on the after-

Test standard CCCT-1916, 7550, tested. hardened with ammonia as described in the upright position:

5% aqueous solution of NH ₃

10% aqueous solution of (NH ^ ₂ CO ₃

Aqueous solution of 7%
(NHi) ₂ SO ₄ and 2 ° / ₀ Na ₂ CO ₃

These samples are then dried. They contain the following quantities of absorbed condensate:

A 16.0%

B 16.9%

C 15.7%

D 13.3%

The specimens are subjected to the char test at the beginning and after five adult cooking cycles. The samples are in an aqueous solution with about 0.2% soap and about 0.2% sodium carbonate Boiled for 1 hour, rinsed in pure water, and then boiled again. The following results are obtained:

A. B. C. D. Initial
Charring, mm
Charring after
five o'clock
Cooking cycles, mm 71
97 71
89 84
84 160
burned

Example2

An impregnation solution was prepared from the following components:

Weight percent

Water 53.9

Trimethylol melamine 7.7

NaOH 3.2

Urea 4.6

Tetrahydroxymethylphosphonium chloride,

8-0% aqueous solution 28.0

Plasticizer 2.5

Wetting agent 0.1

Cotton cloth is impregnated by being immersed in this solution and then until moisture is absorbed squeezed out by 100%. The impregnated sheet is then 90 seconds at 121 ° C dried and heated to 137 ° C for 1 minute. The treated sheet is then placed in an aqueous solution sunk, which contains 7% ammonium sulfate, 3% sodium carbonate and 6% sodium bicarbonate, and hardened. The uptake of condensate by the fabric is 20.6%. The tensile strength in the weft direction of the fabric is 20.4 kg compared to the tensile strength of untreated fabric of 21.8 kg.

The initial charring of the treated tissue is 89 mm and after twenty one hour boiling cycles 122 mm.

The method described in this example can be carried out using other carbamic acid derivatives,

such as thiourea, biuret, ethylene urea or dicyandiamide in place of urea, and / or under Use of solutions of amino compounds for chemical hardening, such as ethylamine or hydrazine, be performed. Similar results are obtained.

Example 3

A mixed-condensable impregnation solution was produced from the following components:

50,

- 'Water 1361

Tetrahydroxymethylphosphonium

chloride, 80% aqueous solution 136 kg

40% sodium hydroxide solution 30.4 kg

Urea 22.2 kg

Trimethylol melamine 28.1 kg

Plasticizer 9,461

Wetting agent 0.571

The total weight of the impregnation solution is 363 kg. A 227 g cotton twill is impregnated with this impregnation solution in a padder at a pressure of 6 t on the pressure rollers. The impregnated fabric has a moisture absorption of 75%. The fabric is then dried in a conventional tenter frame dryer at 137 ° C. for 20 seconds and heated to 149 to 155 ° C. in a drum dryer for 2 minutes. The tissue is then in

padded and hardened in an ammonia-containing bath of the following composition:

Ammonium sulfate 45.4 kg

Sodium carbonate 27.2 kg

Sodium bicarbonate 45.4 kg

Water 7571

Then the fabric is washed in a bath containing sodium carbonate and sodium perborate, rinsed with hot water in a series of open washers and then dried on steam heated rollers. The uptake of condensate on the fabric is about 21.1% · The initial charring of the treated tissue is 102 mm and after 20 boiling cycles 102 mm. The tensile strength in the Weft direction of the treated fabric is 38.1 kg compared to the tensile strength in the weft direction of untreated tissue weighing 40.4 kg. The handle of the fabric is soft and comparable to that of untreated tissue. The shrinkage of the treated fabric, warp · weft, is (-3.0) · (+2.0) and for untreated tissue (-16) · (+4).

Example 4

An impregnation solution was prepared with the following composition:

Water 1631

Tetrahydroxymethylphosphoniumchlorid, 80 ° / ₀ aqueous solution .... 180 kg

50 ° / ₀ sodium hydroxide solution 32.2 kg

Urea 29.5 kg

Trimethylol melamine 37.6 kg

Plasticizer 7.61

Wetting agent 0.571

Compared to a value of 23.6 x 25.4 kg for untreated sheets. The initial charring of the treated sheets is 96 mm, after 50 washes 104 mm and after 100 times Washing 102 mm.

Example 5

A mixed-condensable impregnation solution of the following composition was prepared:

IO

Tetrahydroxymethylphosphonium chloride,

80% aqueous solution 36.0%

50% caustic soda 6.4%

Urea 10.0%

Trimethylolmelamine 7.4%

Wetting agent 0.1%

Water 40.1%

229 m wide black cloth are impregnated with this ao solution in a padder at 61 pressure. The cloth obtained has a moisture absorption of 77%. ^{The cloth is dried at 82 °} C. for 75 seconds in a tenter frame dryer. Then the cloth is cut into four pieces and hardened as follows:

A. B. C. D. 30 curing temperature
temperature, ° C 132
1.0 154
0.33 154
0.5 160
1.0 Curing time,
Minutes

The washing machine is run for 5 minutes, then the solution is drained and the sheets are washed in the conventional manner, but 3.4 kg of sodium perborate are used in the bleaching (5 percent by weight of the sheets) used. The washed sheets are then spun off, dried in a tumble dryer and then ironed. The treated sheets are white, soft, odorless, and the absorption of condensate is 20.5% · The tensile strength of the treated Sheets, warp · weft, is 22.2-24.5 kg in the Then the pieces of cloth in a 20% strength

Hardened ammonium carbonate solution. Condensate intake:

This solution is placed in a washing machine drum and 100 cotton sheets are placed in the drum. After turning for 5 minutes, the impregnated sheets are removed from the drum and spun for 10 minutes in a centrifuge with a diameter of 152 cm at 600 rpm. The moisture absorption of the sheets is around 75%. The sheets are then placed in a steam-heated tumble dryer and agitated for 1 hour. The temperature of the exhaust gases is around HO ⁰ C. The dried sheets are then removed and placed in a washing machine drum, which contains the following solution:

Water 3801

Ammonium sulfate 13.6 kg

Sodium carbonate 6.8 kg

Sodium bicarbonate 13.6 kg

A.
B.
C.
D.

23% 24%

24% 24%

Tensile strength in the weft direction:

A 20.4 kg

B 21.3 kg

C 18.6 kg

D 17.2kg

The hand of the pieces of cloth A, B and C was very soft, that of D a little less soft. Initial char:

A 114 mm

W 99 mm

C 107 mm

D 104 mm

The cellulose textile material to be treated by the method according to the invention can, for. B. in the form of Fibers, yarns or fabrics are present. Wool can also be treated by the process according to the invention although it cannot be called cellulosic material. The inventive method is particularly suitable for the treatment of porous textiles, which the impregnation masses lightly can absorb. Such fabrics include cotton, rayon, wool, jute, and ramie.

Example 6

A. It becomes a solution of 16.2 parts of tetra (hydroxymethyl) phosphonium chloride (THPC) in 16 parts of water. The pH is adjusted to 7.0 by adding triethanolamine. A solution of 11.6 parts of methylolmelamine and 8.4 parts of urea in 50 parts is added to this solution Given water and stirred. Then a 227 g cotton fabric is dipped into the solution and impregnated. The wet fabric is brought to a moisture content of about 65% in a mangle. The impregnated product is then 4 minutes dried at 90 ° C, padded with concentrated ammonia solution, rinsed with water and left in the air dried. The product treated in this way is tested for flame resistance according to the test standard AATCC (American Association of Textile Chemists and Colorists Test) 34-1952. It is found that the ae Product continues to burn after the flame has been removed. The samples are washed five times and Again tested for flame resistance according to the method described above, the burn now as well Samples continue after removing the flame. It is also found that on the surface of the After it has been treated with concentrated ammonia beforehand, the product becomes resinous precipitated white matter.

30th

B. An aqueous impregnation solution is prepared from the following components:

Weight percent

i. \ ΰ ','Υ'Υ". hZ

Trimethylol lamb 7.7

Urinary stump. 4.6

Natrnimhydroxyci. 5.1

Polyethylene (plasticizer) 2 5

wetting agent υ, ι

^{water w} ' ^y

The cotton fabric is dipped into the solution and pressed out to a moisture content of 100%. The fabric impregnated in this way is heated to 90 ° C. for 10 minutes and immersed in an ammonia-containing one Brought solution, which has the following composition:

Weight percent

(NHJ ₂ SO ₄ 7

Na ₁₅ CO _3,. 3

Sodium bicarbonate 6

Water 84

After treatment with this solution, the fabric is dried and tested for flame resistance. Of the The fabric has a char length of 15.5 cm and shows resin stains. The samples are washed five times and subjected to the flame test again. The fabric will burn after removing the flame Further.

C. The experiment B was repeated with the imitate Off * "that the impregnated fabric is heated dried 1.5 minutes at 12O ⁰ C and 1 minute to about 140 ° C before it is treated with the ammonia-containing solution. No more stains are found on the surface of the fabric. The burn length is 9.9 cm,

D. The experiment C is repeated with the off * assume that the impregnated fabric is heated to 93 ° C for 1 hour before the ammonia treatment. Here too stains are no longer found on the surface. The char length is 9.9 cm.

The experiments led to the following results:

A. By treating the textile material analogously to Example 2 of British Patent 882 993, which the USA.Patent 2 772188, was not Flame resistance of the textile is achieved,

B. The impregnated with a solution analogous to Example 2 of the present invention and analogous Example 2 of British Patent 882 993 heat-treated textile goods were initially flame-retardant; after washing five times, however, the samples continued to burn after the flame was removed.

C. The textile material treated with the solution analogously to Example 2 of the present invention was achieves permanent flame resistance.

D. In the case of the impregnated with the solution analogous to Example 2 of the present invention and through Textiles treated with heat at a low temperature achieve permanent flame resistance.

Claims (4)

Patent claims: 1. Method Zürn flame-retardant treatment of cellulose textiles by impregnation with a tetra- (hydroxyorganö) ^ hosphonium halide, a water-soluble, cyclic, mixed-condensable aminoplast former, a mixed-condensable carbamic acid derivative and a bath stabilizer containing the cellulosic acid-treated and hardened cellulose-treated aqueous solution _{Mixture of} substances with ammonia, ammonia-producing compounds _{Q (} j _er solutions of amino compounds that contain at least two reactive hydrogen atoms _{in the molecule> thereby gekeftn} . draws that as a bath stabilizer in the aqueous solution an alkali or Brdalkalihydroxyd, -carboaat or bicarbonate used is and before curing the impregnated cellulose textile both by heat treatment dried and the applied substance * mixture is precondensed until the components the aqueous solution have passed into a product which is insoluble in aqueous ammonia * solution. ₂ . Process according to claim 1, characterized in that an aqueous solution is used which contains about 10 to 40 percent by weight of tetra (# - hydroxyorgano) phosphonium halide, about 5 to 15 percent by weight of aminoplast former, about 1 to 10 percent by weight of carbamic acid derivative, for example Contains 0.25 to 0.75 equivalents of the basic inorganic alkali or alkaline earth compound per mole of phosphonium compound and about 35 to 80 percent by weight of water, 3. The method according to claim 1 and 2, characterized in that the impregnated cellulose ' material is heated to about 93 to 160 ° C for about 30 seconds to 1 hour. 4. The method according to claim 1 to 3, characterized in that the curing of the product with an aqueous ammonia solution or with an ammonium sulfate, an alkali metal carbonate and an aqueous solution containing alkali carbonate is carried out.