BE463685A - - Google Patents

Description

       

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  "Process for rendering fibrous cellulosic or protein-based or other similar organic fibrous materials resistant to flame, as well as products according to those obtained by this process".



   The present invention relates to a process for rendering cellulosic or protein-based fibrous materials flame resistant to other similar organic fibrous materials, and in particular textiles. such as, for example, fabrics for clothing, heavy canvas, tarpaulins, draperies, etc ..., while substantially retaining the primitive hand and touch of the fabric and avoiding the consequent sacrificing of a part the resistance or solidity of the fabric.

   For best results to be obtained, the end product must be durable and withstand water, repeated washing, soaping, dry cleaning, and although it burns when
A flame is applied to it, combustion should cease as soon as the flame is removed, and there should be no unwanted decline.

   The invention also relates to procedures of the type mentioned above seventh to give cellulosic fibrous materials or similar organic fibrous materials a certain resistance to the action of humidity,
The inventors have discovered that one can obtain a

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 finished product having the above characteristics by processing
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 Dbtire with an enene acid such as ortho-phohoric acid and with a soluble organic base containing nitrogen, such as urea, where it is described hereinafter. Applicants do not i-norent that Qrtho-phosphoriu8 acid and various phosphates have been proposed heretofore to serve as substances intended to render tissues non-flammable.

   It has already been proposed: also to react phosphoric acid and urea, to dissolve the reaction product, to impregnate and to dry. To the best of the knowledge and belief of the applicants, none of these methods has produced a product which can be used successfully in commerce, the product
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 finish having the disadvantage, or of not resisting in a durable way 1 water, soaping or dry cleaning. who
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 are faohauseaent distinct from the hand or the solidity of the product, or lend themselves to criticism in other respects.



   According to the present invention, a process is obtained which makes fibrous materials of the type
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 ao. having cellulosic materials or the nature of the protein and mixtures of these materials, as well as giving a certain resistance to the action of humidity to the fibrous cellulosic materials, this process being characterized in that it consists to subject matter to the action of a solution
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 aqueous of an acid giving the product a great resistance to flan:

  ae, or of an acid giving great reslatance to the action of moisture, and of an organized soluble base oon- 3 nating nitrogen, to remove the matter, to heat it until 3 sufficient temperature and for a sufficient period of time to give birth. chemical combinations with the material, t introduce groups of acid and nitrogen into the complex, then wash and dry the material thus treated, the acid or the acid and the base being present in the

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 solution in sufficient quantity to produce good resistance. the action of humidity or flame, and the pH of the solution being such that the material treated has a pH varying between substantially 3 and substantially 7.



   In the following description, special reference will be made to cellulosic materials. However, applicants have found that when protein-based materials, such as wool or silk, are subjected to same chemical and physical condi- tions, the product may be given satisfactory and durable flame resistance properties without undue damage to the hand and the strength of the fabric
The treatments described above make it possible to obtain a combination (that is to say a compound) with the cellulose,

   combination whereby the finished product is made resistant to water and repeated washing. Applicants believe that during processing an intense esterification of the cellulose occurs, the acid combining with the cellulose and with the nitrogen-containing base (or with products formed therefrom), to give a complex which is durable to subsequent leaching, soaping, washing and dry cleaning treatments. By combining with cellulose, the acid apparently carries with it, in the complex, the nitrogen-containing groups originating from the base or compounds derived from the base during processing.



   A combination of cellulose, phosphoric acid and base occurs; This is evidenced by the fact that the fabric allows for a clearly determined quantity test for both nitrogen and phosphorus after the finishing treatment, which includes washing and drying after the first treatment. Subsequent washings remove only negligible amounts of these elements. so one can get. after repeated washing, satisfactory quantity tests

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 fear both azate and phosphorus, which proves that
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 Pro, durable flame resistance riatr3s are produced by the presence of phosphorus and nitrogen in the complex.



  If we consider for example the case of the urn, among some of the bases that can be used, we find that, among
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 Very functions, urea seems to play the role of a buffer for phosphoric acid to exert a softening effect on the tissue, so that the latter retains much of its pre.aière resistance. This is also true for other similar weak bases, if they are present in sufficient quantity.
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 When the treatment in question is applied to woolen fabrics or to fabrics containing wool, a combination with wool is obtained.



   According to one procedure, the acid and the base can be mixed in the cold and water added. The resulting solution or mixture is taken and applied to the tissue with a tampon or any other: .. rent: usual, then we dry the tissue
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 If prepared, drying preferably takes place on a binder and treated, the treatment giving rise to the conblnaison with the cellulose, 00? ibi; iaisotl as described above, and both in terms of temperature. and i. duration, as will be seen later, so as to produce the combination and to substantially preserve the solidity of the fabric
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 The fabric is finally washed in hot water and dried.



   According to another procedure, the mixture of acid and base is heated to. About 88 C, Or cool it, add water
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 and we apply the.solution or; dan, 3rd OOItU.1e pNoéden; #nt.



  In this way they formed genera of the counterparts of the mi-aQniac and complex cOl, the nitrogen coming from the base, and the solution or the mixture are more approximately neutral to the : QO:! L6; lt of the application on the fabric, which tends to

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 to avoid attacking the equipment. Higher temperatures and longer treatment times can be used, which makes it possible to obtain solutions of a substantially neutral nature.
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  In some css the external heating is not necessary the ingredients react spontaneously in the solution and. cooling. being thus sometimes necessary for.,! ,, Icr the reaction. Other times the mixture can be heated for a short time, when exothor reactions occur. miquea requiring cooling of the mixture to settle the. reaction.

   
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 In such a case, the heating will result, as will be described later, that the original compound or the original nitrogen compounds are dumb to some extent and transformed into new compounds and generally more.
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 oàmplexes. Of 1 * amraoni-quo is often released during these reabsorations, tTn., another process consists of melting together the troîdu and 7, a'b ,, to cool * to add ltet..po.5.s to operate as indicated above,
Although the solution is generally applied to the '
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 tissues and at room temperature it can be safe, if desired, at somewhat higher temperatures.

   At the tempera.
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 tarea more haunts' one generally obtains a ^ greater solubl. ity of ingredients. 0,: oi is very profib; .b1 <? and in some cases the solution can be applied almost boiling on condition that no noticeable effect results as it will be 5zd.LCjité Ci - cprS.



  During the drying, which is done like alhabîtudel, it was necessary to eliminate of the, mn *, 3 .-, rn d; berucoup most of the water and for this purpose 'the applicants have found, this not being given any-
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 As an example * it suffices to pass the fabric through a drying atmosphere of 150 C. The fabric remains in

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 the dryer for about 30 seconds, but it only reaches the temperature of 150 ° C for several seconds.



   The treatment temperature must be carefully regulated.



   It must be high enough to ensure the treatment, that is to say to bring about the chemical combination, in a practically limited period of time, but it must not be high enough for it to occur. results from undesirable alterations in cellulose and a corresponding reduction in tissue resistance. The duration of the treatment is related to the temperature, as can be easily understood: the higher the temperature, the shorter the duration of the treatment, and the lower the temperature, the longer the duration of the treatment. .



   As will also be seen, there must be enough acid and urea (or other usable base) on the material to ensure the presence, in the finite material complex, (o est of material treated after having been washed in water at 820, for 10 minutes for example and dried), a sufficient quantity of the basic element of the acid and nitrogen to give the desired results. The quantities of matter and the period of time as well as the temperature are in an important relation between them.

   By way of example, the applicants have noticed the following when a piece of cotton fabric is treated with a tampon with a solution containing 130 gr. ortho-phosphoric acid (75%) 180 gr. of urea and 340 gr. of water (molecular ratio of 1 for phosphoric acid to 3 for urea and 15% phosphoric acid in solution), squeezed out as usual, (giving approximately an absorption of 100 of the solution by weight), and dried:

   a) after a treatment of 120 minutes at 120 C. the tissue has

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   Good resistance a. the flame after washing in water at 82 C for 10 to 20 minutes, but this resistance is only weak after soaping for 15 minutes in 1/4% Igepon T at 82 C, 100 parts of an Igepon T solution for
1 part of fabric by weight b) after 120 minutes treatment at 125. the flame resistance is excellent after such washing with water, and it is still good after similar soaping: c) after a treatment of 120 minutes at 13010-the flame resistance is excellent after such washing or soaping ;

   d) after a treatment of 60 minutes at 130 C, the flame resistance is excellent after such washing or such soaping: e) after a treatment of 30 minutes at 140 C, the flame resistance is excellent after such a washing or similar soaping: f) after a treatment of 10 minutes at 170.0. the flame resistance is excellent after washing or soaping:

   g) after a treatment of one minute at 205 C, the flame resistance is excellent after washing, but it is only good after soaping *
Now if we reduce for example to 6.9% the amount of acid contained in the solution, with the tern absorbing solution on the tissue, no result is obtained, while if the tissue is treated at 170 C. for 5 minutes, good results are obtained, even after washing or soaping.



   Within the range of processing temperatures just mentioned, applicants have found that the best results are obtained for most commercial applications at temperatures between 160 and 180.0. At these temperatures. the duration of treatment will vary between 15 and
3 minutes.

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    The reaction to this 11 close actually takes place from
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 on the acid side (lower p.1) rather than on the basic side (upper pn), the fold is in this case by means of indicator solutions applied to the treated tissue. The applicants have found that between the values 2 and 7 for the pH on the treated fabric (before washing), satisfactory results can be obtained. The value given for the pH on the fabric varies between 3 and 6. The duration of the finished product will vary slightly, as we already have. said, but a pH of 3-6 gives satisfactory results in general.
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  Other.Tent, the pi of the solution before the application is not very important, because it can be adjusted as needed by the addition of bases which will volatilize during the treatment leaving the pH on cellulose to an acidic value such that operation reactions will occur during processing as described above.
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 Among the volatile bases suitable for adjusting the pH of the solution, mention will be made of α :: fJJ.oniom hydroxyl, dietylamine, and isoplnpylalin. For all practical applications, 4eammoriium hydroxide is sahi8fa18ant.

   In any case, the amount of base added to make the pi of the solution is very small, the solution generally having, by itself. a pJ of a satisfactory value '- Of course, if. the pü
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 is too Qlevtt ,, one can, to adjust the pzT of the solution,
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 add an acid giving resistance to the flame. In g ":( l (l- ral, all that is needed with regard to the pH of the solution is that it should be such that, during the treatment)
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 ment, the piI on the tissue is reduced and reduced to the values mentioned above.

   Usually, for the solution, a ph whose value is about 1/2 greater! T. that of the fold of the treated fabric will be satisfactory. It is possible to go further ... provided that the pH is reduced, during the treatment, so

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 to give the treated tissue a pH having the value indicated above.



   The pH value on the fabric during processing to some extent determines the speed or rate and degree of the reaction between the acid and the cellulose. The more the
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 pH is low, the faster the reaction is complete t, and the higher the piifst, the more the reaction is $ tÙ and; .loiC1S it is compote for a given period of te; ps and 'a .te ,;

  1p erature given for the treatment. The same. for a given pH, the reaction can be made more complete and its extent increased by increasing the treatment time, the treatment temperature or both. For example, for a pH equal to 3.5 a duration of
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 treatment of 4 minutes and a temperature of 165 ° C may be necessary for a given degree of golden color to be obtained, while for a ply equal to 5.5, a hard milking
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 8 minutes may be necessary, for a temperature of 165 C to obtain the same degree of duration. In addition to the pad application mentioned above,

   the solution can be applied to fabrics by any of the methods known in the textile industry,
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 such as sprinkling, sieving, printing, coating, etc. Whatever method of application is used, the fabric is dried in the manner indicated to remove most of the water .
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  The concentration of the solution itself is not critical and depends on the number of applications, but the last grip on the finished fabric is 3mportar; te. far exe11Dle. when the solution is to be applied to the fabric in a single pass and thoroughly, a solution containing about 30 kg of active solids will be sufficient, depending on the weight, absorption capacity and purity of the fabric, calendering after impregnation, etc, ... This. with an absorption of

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 iexxible solution: 8, t '-equal to 1ÇÇJ "PI daonera on the finished tU66U u <ie last" take "(chi.iique take by combination) of about 8 k about 30p of, .steres saddled, which is a take for which the dea, .a: deurs Qnt found that it gives general results satls-'ai.s, z, -, ts in all respects.

   One can be con tempted to take small peaks, s. condition ciue we only want a bc ... resisted: loe the flame. Taking more than J0% has no significant advantage. The last take falls to these figures owing to some loss during the
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 treatment, and further loss during washing (which
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 li.,. i-; e soluble chemicals which skip in excess).
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 If one wishes to make a certain number of impregnations and
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 separate dryings, Or can employ an extended solution, the number of passes dpe; da: t of the desired dilution 'for example, with a solution containing from 2Q to 60 of! 18.
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 the desired results can be obtained for example in two
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 passes and g aeralea; i1t in three passes at most.

   The last take of el .: e: t basic acid and arote in the fi 'binds matter (atest -; - say treated, washed and dried @), is i.lpOJ: t8, te, a1: .if we will see it later., As for the acids, it is orthcpnosphoric acid (: 6. # 4) which is g.dl'ale. :: e (lt the most satisfactory. However, any acidic acid by which the tissue has not been rendered inlaid can be employed, eg, pyro-, phosi: hor3que, crthophosphorous, pyraphosrhorous, sulfuric acid and acid.
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 phytic, under / ëserve of the ccnditicn indicated above.



  It does not coml, ient to use acids which are eaewaaiv, ent volatile under the conditions of the operation, or acids creating conditions ,, a or produced chemicals having an excessive degrading action on the skin. - lcse, such as active oxygen or "alc8; eras au-tifs. Thus
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 hydrochloric acid is not useful and nitric acid is not

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 not rec-0.11TlJ8ndé. although the latter can be used together with other acids such as ortophosphcric acid, as shown below,
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 It is the aarzobs.s3, ues acids which give the least satisfactory results and the dibseic acids although .m.eillet1rs. are not as good as polybasic acHes, as will be seen later.

   The so-called polybasic acids containing excess atoms of the acid element have sataiai- S811tS "in particular when they are of a pol7b * 4'8 nature. These acids are known to be beautiful, in particular of the phosphorous type,
Salts of the acids can be used, provided that the
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 The base of the salt is volatile under practical conditions, or that it takes an active part in the operation. Among the first we can cite ammonium phosphate. dïmdth3.a: i.ns phosphate and isopropylamine phosphate: among the latter are guanidine phosphate, guanylere phosphate and urea phosphate
Acid substitutes can also be used, provided that the substitution groups do not destroy.
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 not jump the properties of resistanae lh the flame.

   Examples of exer.nples include sulfamiue, phosphasic, diarninophosphoric acid and hexa-phospharleue nitride. Other acids of a complex nature containing arte and phosphorus could have been used, provided they were strong enough to combine with the fibers in question. However, most of these acids were not , are not commercially available. We
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 can use the so-called orsaf1iLJes esters 8. Provided that they do not contain an excessive amount of (,, tree and that they do not evaporate the acid group to form the desired combination with cellulose- lvr For example, P-ono-methyl-phosphoric acid can be used.

   Substitute acids

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 kills ps haloes not r4e nt pa'B, except the fluo-phosnhori fue acid, because of the instability of halogen groups in solv.ticn and on the tissue - Qucnt aLx organic bases, for which it is desirable that they are always present in excess, they can:.: be weak or energetic * However, when the acid used in the operation is compared with the nitrogenous bases,
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 aeiies -; <1 all have a distinctly basic nature, the distinction between weak bases and strong bases <; te.:. t based on how they behave in the solution and pe. .during processing * i8r exe..l le, if there is a notable change in ,, i the cone: .1trll tio ..! of the base r brings no chs:

  1 [e.ellt appreciable in the pal of the solution or in the p: 1 dL treated tissue, we say that the base is weak., Toutefcis, if the., Ê :: e cua.ge:;.ent causes clear : ú8nt a change in the fold, the base is said to be ",:. esique. 011 can for example add it in excess to a ready-made solution without varying the fold appreciably; on the other hand, if in addition of the guanidine in excess to a very first solution
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 p r6e, the p, 3 will increase noticeably.1,: t, and if the amount added is sl; fZisa; lte, the solution may become so markedly basic that satisfactory results will not be obtained.

   In other words, with strong bases, any excess should be such that it does not pass the treated fabric (before washing \).
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 net "lerlt dJJ coto aoide. hàrrii l.es weak bases which can be used, one will quote for example the urn, the biuret, the cianao,; tamide. the Bemi- carbaziie, the dicysndia., lde * ac ..: ta! .1ine, la:! orma.; 1Ú.de and r;} wla, 1Ïn6. In .7ertai ', s c'as, when the solez6âüitr of the weak base is not gr8 :. de, even: l6 in hot solutions, this base should not be used alone and is effectively used in conjunction with one or more other bases.

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  For example,. melalQine is not sufficiently soluble in phosphoric acid to produce a good working solution. However, it can be used, for example. joint with urea and then gives a good working solution.



   Salts of these bases can be used in part with
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 an acid resistant to flame, eg> 1? sulfates, phosphates and sulfates; in such a case "1 (.ide introduced by the base replaces a corresponding quantity of acid in the formula of the solution.



     Base substitution products can be used
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 weak, such as those which contain amino, hydroxy, halogen, or organic groups, provided that the essential characteristics of the things which make them useful in the operation are not destroyed.
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 alpha-gen 6 and hydroxyl groups may increase the basic nature of the base to such an extent that the weak base becomes a strong base and it is necessary to use it accordingly. urea is a weak base,
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 but iuiûo-tre (guanidine) is an energetic base.

   Halogens tend to. create a complex having a halogen in their constitution and this is not particularly desirable
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 due to the instability of halozerated oraposes, organic groups containing carbon can be introduced,
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 but they tend to reduce tissue resistance at 18 flaz., e. an can use a cO: 1JpoSé such as net 1-ur:

  e instead of urea, but in the face of it, does not gain much We can worsen <i-1eL'giques bases, but poiyme energetic bases risk causing the solution to pass to the aloaline side 8i they are used in aXi notable, they should be used Cé) llJot, tê) t! i \ t IV! \ "I) III tn j, 1.i> via <u bF \ UB weak. 'In addition, weak bases c, - t have an amcr-

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 weaving with respect to acid and cellulose, which is not the case also .. marked with energetic bases:: and CO: 1e a clear action;, e, .ta: .ortissa ; tee, at dâsir: ble to allow the adjustment of the reaction, i and for dear everything
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 inopportune softening, it is preferable, for this reason
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 its also, to use the linergic base only con <j / C'inte: ent with U'-16 weak base.

   It seems that what happens is the co, bi, .aison of the weak base with the acid is r6r ::! 11a'ée during the treatment .t, which produces an oertata arliOrti.sSe [19nt or The slowdown of the reaction. The amount of ergic base must be insufficient to polish satisfy all the acidity of the acid during the treatment <The use of weak bases oonjointeizent with éGergi bases., [ This results in the final product having a greater resistance to weak bases with a heavy base containing a considerable amount of nitrogen added, as an effect of not only allow the adjustment of the pl and ensure a damping action, uais also of tou m3r, eo:.;: e will be seen later, a r4nde
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 nitrogen that can enter the phosrhore complex
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 nitrogen-cellulose, which increases the durability of the product.

   J; 'ar: i
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 the energetic bases that can be used, we will quote here
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 guanidine, la; arbohydrazid3ne, dihydroxygu8úidine, guan; jllUrd6. oxalarnidine and biguanidine.



  Qn 1 reut uses co.'l} ', base substitution cses
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 EMI14.9
 e! ergi't) '8. Additionally, these substances have satisfactory solubility in solution and are reasonably stable after being removed from the tissue. These c-o :: 1f'C St,; S of Sl'b; titutiol. sō t substitution products al.1inogenated, hydroxygen-s, halo us and crGaGiqIJe radical 'This last type of, :: 0.'1 c 86 must not r, fs eonte :: ir de roupe; chains of carbc-, e eg, es, this being detrimental to the resistance 'f. 1 P,> 1 a, - ,, Ie -

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   Salts of energetic bases can be employed with
 EMI15.1
 volatile acids, deoo :, osable or weak, such as;

   for example, guanidine carbonate, amn6 acetate, guanylurea formate, and biguanidine borate. Guanidine carbonate is useful and has been used extensively for use 1-rode (, tion on a large scale.



   It is also possible to use energetic base salts and
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 acid providing resistance to hâril11ê, such as, for example, guanidine phosphate, guanyloure sulphate and carbahydrazidine pyrophosphate. 3h in this case the acid part of the salt replaces a part of the acid in the formula of the solution-
 EMI15.3
 The general conditions for the base, whether it is a weak base, an energetic base, or a mixture of the two, are that it must be water soluble, react with 11-acid. so as to introduce nitrogen into the phosphorus-cellulose complex:

   it should preferably contain more nitrogen than carbon, and when one employs at least several energetic bases, there must also be a
 EMI15.4
 weak base in presence, generally retains in excess, to facilitate :): 'the adjustment of the r: action by producing the desired damping action between the acid and the cellulose. Weak bases produce a damping action due to the fact that they compete with cellulose for acid.
 EMI15.5
 for which it is advisable to use a berry containing a lot of nitrogen and little carbon, it is that the greater the quantity of carbon present, the lower the inflaù-1ùability.

   It is for this reason that ur; .es sL1 ;;,: titues and other nitrogenous compounds containing relatively large amounts of carbon are not profitable when optimum results are desired;

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 W g :: ral les aei;, a ,, àeuri se j, ioi; cxe-1t to introduce the pl: .s of nitrogen possible and carbo-ie care possible in the acid-this Llulose. This nitrogen must be the strongest fixiî. pcs;> ible and should not be adversely affected when the fabric is subjected to dexivating and soaping treatments, it is important that this excess nitrogen scit i..it; fc'3uit by a weak base due to an energetic base: cn has tatu tutetois that it is almost impossible to obtain a cc..r lexe base faiole - rcé nitrogen had a great sclulity; in the .¯.la, e in reaction.

   Afraid to obtain such lubricity as it is bo, to operate with nitrogenous coacsés with the lowest roids, such as urea, ae t a, ii de cu la fo r ,,; a;>, 1 de, In the case of eueric bases, which does not come out in excess, lending itself to arbitrariness, as we said above, the solubility must is not such an important factor. , tiel, because these bases do not scr: t not used,; es in relative quantities.;, e, t large, and there are only a few eā ^ ui os3s having a high nitrogen content and a low carbon content.



  The analysis showed that with a 6-, ergic base rich in nitrogen, a greater part of nitrogen enters the cc., Lexe.



  For example, if urea and phcopheric acid are used, the atomic ratio of nitrogen to phosphorus over
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 the finished fabric can be 1 part nitrogen to 1 part phosphorus,
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 while if the oa uses u, i m61s: rod of urea, guanidine and pho, 4- 'hccic acid, the ratio is 3 parts of nitrogen to
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 1 of phosphorus, indicating a notable increase in
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 nitrogen, an increase which is due to uanidine, During the
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 heating the solution or during tissue processing, many changes may take place in the bases
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 nitrogen and, in general, the resulting co. ,, Ilex contains u ,, ..el, .e of nitrogen. It is therefore not possible to

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 give the exact composition of the complex formed.

   For example, dicyandinamide forms a significant amount of phosphate
 EMI17.1
 guanictina when heated with phosphate .- :; 0} 10- or dl-ammonia, dieyandiamide and phosphoric acid form a significant amount of guanylarea phasphote, and when disyandiamide and guanidine are heated together, they can form cyanogen, biguanid and nialanil. This formation of complexed nitrogenous co-compounds facilitates the achievement of good flame resistance. as well as
 EMI17.2
 increase in the duration of the resigtao.e water, since the compounds thus formed tend to increase the stability of the
 EMI17.3
 Gcmp la x As far as CO! 1 is the solution, it must be from yr:

  Clear rance to ensure better penetration into the znatiîîe make resistant a. flame and aation more uniform over this material.When it is phosphorus acid, the quantity of acid should be such that the quantity
 EMI17.4
 of phosphorus remaining in the fabric resists Infla * aie after the final washing and drying is preferably varied between 1.5% and 4.15. Below this percentage, generally only poor flame resistance properties are obtained, and above this percentage little is gained.



   If we consider once again the last take and
 EMI17.5
 if orthophosr, eg horic acid, is used, the necessary percentage pocr make a delicate tissue. the flame also depends on the amount of nitrogen water J? reSêl1C) e For example, if the nitrogen content of the finished fabric is 2%, the amount of phosphorus needed to provide resistance
 EMI17.6
 effective at. the flam :: is about Z. 85%, slums only if the quantity of nitrogen present is 3%, the quantity of phosphorus can drop to 2.8%, the resistance s. la la: soul, obtained

 <Desc / Clms Page number 18>

 
 EMI18.1
 dars these CO .ditio: s, wbe, ib 8ücore satisfaiSB, te.

   If the content e., Nitrogen tc: be at a very low figure, for example down to a small fraction of 1%, the resistance, the flaénl # will be ù> edicres,? .E! Ne if the over-antage of phosphorus present is + raised.



  The nitrogen content should vary by prafarel2ae between e, ivircn C ;, 25; et and about 6%, and the preferred limits for the content of: ho ;; hore is about 1% to 5; b. There must be enough
 EMI18.2
 acid and base present on the weave during processing
 EMI18.3
 L ,, e-, t can ensure this final chemical edition. Below C:, 85 / o of nitrogen, the ir.flu8uc8 of the 81st, 1t becomes negligible, and above 6'o of azcte, due to this we obtain an excellent te the usist [1,. this to the fact I, it that the au does not gain anything from, erti0Llter. Below O.5 of phosphorus an excessively large quantity of nitrogen would be required. The percentages shown above have been worn after application of the solL.tion and after the fabric has been treated and washed with. bottom in very hot or boiling water.

   It is the percentage in this final product \ he is important 'Previously, losses
 EMI18.4
 determined and measurable take place during processing. he
 EMI18.5
 esanature bound of course - and if additional ingredients were introduced; J, e'1taires resisted 1, 118- "r.6, this had in + cause a corresponding change in the chices ratio sai re
 EMI18.6
 between nitrogen and phosphorus to give a final product
 EMI18.7
 satisfactory. For example, if a halogen such as chlorine is introduced to make the flame resistant C071I free, the amount of the other ingredients may be reduced.



  As stated above, however, the introduction of a halrgèúe is not particular. Nc, t desirable, because of the instability a. l8 solar irradiance,, heat and humidity, which releases halcidic acids. However, one can obtain a 1.:. the etoistance of the incat1descsce with a content of 6; i phosphorus falling up to. 0.1%.

 <Desc / Clms Page number 19>

 



  Since wool and the saw contain nitrogen,
 EMI19.1
 sulfur and phosphorus in their C Q, 1 / f'OS natural chemical ition, the above correct figures should be considered
 EMI19.2
 as being in addition to these u, ldL2ts -existing natural deny.



  The cellulosic materials treated with this frondate not only have aarac, tarrJstiqlJ6s flame resistance properties. they are also clearly resistant to rust, pitting and other effects which add a
 EMI19.3
 valuable to the final product. This is not the effect for protein-based tissues.
Cellulosic materials treated by this process
 EMI19.4
 may be prone to swelling when immersed in water for a long time.

   In some cases this property is an advantageous asset, but if it is not desired, it can be achieved by erl4ant an aldehyde and this swelling property can also be reduced by modifying the hydrophobic nature of the tissue by a subsequent treatment. by means of formaldehyde or agents by which the product is made impermeable to water. It is not appropriate to treat fibers,
 EMI19.5
 protein using ald2xde.



  This process can be applied to fibrous materials which have previously undergone other treatments, such as leaching, moteerization, parchinining, printing dye and finishing treatment, for example. provided that the particular treatment is such that it does not ') O; .J1- cte as the resistance to flame. Another treatment such as a primer treatment, a treatment intended to make the product 1; 1 # waterproof, a coating: 1eút and a medium finish can also be applied. for example, after having multiplied the agent ensuring the resistance to the fla;? xne, provided that these triumphs do not destroy the resistance, the flsipme. 'Such a slJpplê treatment; #ntaire is not part of this

 <Desc / Clms Page number 20>

 
 EMI20.1
 inve .tio ;.
 EMI20.2
 



  Co .. ,, e cn has to be ,, king ,. to use neither resin, nor: plastic material, neither plasticized, nor.,: soluble in a solvent to produce this finishing agent, an exoe: lezae duration is obtained for the dry cleaning solutions
 EMI20.3
 In all the examples given below, we have considered
 EMI20.4
 that the finished fabrics are very durable and very satisfactory from r.; sistsrc; e 1 ;, the flarcity when fabric samples treated, after being subjected to the following series of 4 tests, and after having been kept qerbiral>, ie, b in an arrow for 10 seconds, do not oo.itinuai8nt. burns:

  -.
 EMI20.5
 a) after washing for 24 hours in distilled water,
 EMI20.6
 b) after 1 / S hour of boiling in desiccated water, after a bath of 15 wiúutes in a soil, brand of Io-eï, o, T at 1/4% at C2C, 100-1, followed by two rinses in
 EMI20.7
 hot water
 EMI20.8
 d) after uii treat M'one hour with a solution of
 EMI20.9
 Stoddard dry cleaning solvent;
 EMI20.10
 e) after a one hour fermentation in a Saxhlet extractor with dichlorodiethyl ether.
 EMI20.11
 



  Of course, a separate strip of fabric must be used for each of the above tests.
 EMI20.12
 



  LWLilJV 1.



  Cn a. applied to the fabric, at ta: .pon, a mixture of water co.teüE.nt 49, 'µµ urea and 18.4% crthophosllhoric acid (lOQ1
 EMI20.13
 ,,
 EMI20.14
 in 1 Gide guiding the ra ,, po., t of 2, 7 parts of urea to 1 part of rie acid, ue, the tissue (crcis) was then dried 1.



  15 ° C., on raze for about 3 seconds as described, then the .chu fabric was treated with an oven at a temperature of 175 * 0 pc. In 2. Added. The fiiî tissue had the above rzP.ti.oinea characteristics. All trnite.nent sei1sible; 1eLt plus lo:, g, tc ',' t en au; :: e, tar, t la dur <Je. would reduce the risisbanae

 <Desc / Clms Page number 21>

 traction.



  EXAMPLE 2
 EMI21.1
 The merle melasse was applied to the t "l:; r'o," [on the fabric, which has at ':. then dried as described and treated at 15 g for 15 minutes. The test of trxitezext being there read low, it was necessary to make the treatment last longer to obtain the third result. (One obtained the desired fi-ii. Rar le
 EMI21.2
 The result is understood to be the obtaining of the finished product resistant to marl tests. This is true for all usable bases, weak or vigorous.
 EMI21.3
 



  'E "' L '3 Lel" 1ê: ne m ,, ùange was applied to the tB,: 1! 10 .. on the dry fabric as described, then the dried fabric was treated.
 EMI21.4
 k 140 ± for S3 minutes, the necessary time for processing, in order to obtain the same result, being even longer due to the lower temperature. The desired end product was obtained.
 EMI21.5
 



  The temperature of 14060 used in this example is very close to the lowest possible temperature limit.
 EMI21.6
 so that the operation can be helped to successfully complete within a reasonable period of time., 'Considering the duration of the treatment, for example jesj¯u'h, about 45 ndnLtes or a little in addition, one can reduce such a practice to a number a little below 140 * -0 However, as stated above, lower temperatures can be employed for longer treatment times. Thus, with a te: y: rature of 18C G and a treatment time of 120 minutes, or. Can obtain good results, provided that use r; c; -ctentrati.m, ade- quate is used. .

   A sensible temperature of 120.0 appears to be the lower practical limit for a typical apparatus This is true for all bases usable in the process.



   Except where indicated above, the ratio between

 <Desc / Clms Page number 22>

 
 EMI22.1
 weak bases such as urea and phosphoric acid
 EMI22.2
 is not artti'iue, as we will see from the following excels, its.



  Ale. THE 4.



  Was applied to the fabric, at tn .po.â, an inela, rod of water containing 66.4% urea and 16.6% phosphoric acid (100) by weight, i.e. a ratio of 4 parts of urea for 1 part 9'acid phosi, hori ,, ue, then the tissue was 8ahé k 15C * C pe .dar.t about 30 seconds in the way daerite.h1 ooaz- appears with the axis.'aple ? it will be seen that the increased quantity of urn, fear w xed te ';' l ,,;, ature of treatment of 15 OC requires a longer lapse of time to carry out the treatment and obtain r le J: ê: r, e result.



  The product obtained had the characteristics criticized
 EMI22.3
 upper*
 EMI22.4
 & ± 1.2L ± 5.h; 4 applied to the ta'pon a mClaAge containing 2OE $ urea and 2 ±> # orthophesrhoric acid (100 ") by weight, that is to say a
 EMI22.5
 ratio of 1 part of urea to 1 part of phosphoric acid,
 EMI22.6
 in the manner described and treated at 150 ° C., the time required for the treatment was obtained for 13 minutes. In a4.iarr.nt with example 3 cn sees that with the smallest! U; 1tity of urea and in Maillten, 9J1t substantially the same ccnce-n-
 EMI22.7
 
 EMI22.8
 tration for: tphosphoric acid, the duration of the treatment can be reduced,: e, t while obtaining the same result-
 EMI22.9
 The final product had the characteristics described above.
 EMI22.10
 



  What can be seen by what precedes that when the te: igçurature of treatment leads the necessary duration fear the treatment increases: ;;, - e, 1te.We will also see that the higher the report, and by cc .SégC8ut, the more the protective inpïuenae of the east urO. the longer the duration of the treatment will be, without

 <Desc / Clms Page number 23>

 The lower the ratio of urea to phosphoric acid and the less the protective influence of urea, the shorter the duration of the treatment must be.



     Considered from a practical point of view, a. The ratio of 4 to 1 by weight of urea the phosphoric acid is about as high as possible without causing harmful wastage of urea. This ratio can be increased to, for example, 10 to 1 , a figure at which losses become prohibitive. It is of course understood that in all the examples given the fabric is washed after the treatment and that all the urea which is not necessary is removed by washing, only the proportion of urea which goes into the combination remaining in the mixture. tissue.

   Densors prefer to use 2.7 parts of urea to 1 part of phosphoric acid (known as a ratio of 4.4 molecules-grams to 1), but a slightly lower or higher ratio can be used, as is the case. said above.



   This applies to all usable bases. With energetic bases, as has been said, care must be taken that the solution does not become distinctly basic-
The degree of permanence of the finished flame-resistant product depends, among other factors, on the concentration of phosphoric acid in the solution.

   As the following examples show, this concentration can be varied. between very wide limits, according to the desired permanence, on condition that the quantity of urea or of one or more other weak bases present is sufficient to ensure the necessary protection, and on condition that it? has a sufficient amount of acid and azcrite groups present in the complex, as stated above. This is also true for other acids which can be used in

 <Desc / Clms Page number 24>

 the @ rocédé.
EXIPLE 6.



  A water mixture containing 30% is applied with tanpon
 EMI24.1
 urn and 30jb phoSlhori'iue acid (10f) by weight, or one. ratio of 1 to 1 between Jurys and phosphoric acid, we have
 EMI24.2
 8 '-. Oh as described and processed at 15Q Q for 12 minutes. atXi.9Ll 7.



  Zr, a applied to ta o. a ..nla.lge of water containing 5 orthc- of urea and 9.3% acid / phosphoric (100%) by weight, i.e. a ratio of 2.7 parts of urn per 1 part of phosphoric acid
 EMI24.3
 However, it was dried as described and treated at 15 ° C for 2 minutes.



   In the two examples above, 6 and 7, we obtained a
 EMI24.4
 The durable and fluff resistant product was not satisfactorily, but the strength and smoothness properties of the fabric obtained in Example 6 were slightly better than it. those of the product obtained in Example 7.



   EXIPLE 8.



   A containing 49.6% urea and 18.4%
 EMI24.5
 of orthophosphoric acid (1C'0%) by weight on an octca fabric which was then soh on a ream. The dried fabric was
 EMI24.6
 then treated for 1 minute 20,500 then finally $ 1 go with water and dried.



  The ; final reduction thus obtained had the indicated curacterial w higher.-high%
 EMI24.7
 Lll.ù%%; 1WJ ::. :: IE We have.: 318.ng8 1CC? parts of urea and 50 parts of orthophospheric daaalde (75%) by weight, then rapidly heated to 170 * 0. The resulting mixture was cooled, first added 75 parts of water, then 7 parts of alpha 1: 1 mg hydroxide (2) and 10 parts of formaldehyde (<7%). In this example and in the following, all parts 1, -., Diquees are by weight.

 <Desc / Clms Page number 25>

 



  The resulting solution was clear: it was impregnated with
 EMI25.1
 a cotton fabric (twill) by passage through a conventional textile impregnation calender, the operation of dipping the fabric into the solution and then squeezing it to remove excess solution therefrom. The fabric was then dried on the ordinary running ream, the temperature being
 EMI25.2
 About 15,000 The fabric was left on the stripe for. '' long enough for all of the water to evaporate.



   A part of the cotton fabric was treated at a temperature of 175 ° 0 for 8 minutes and 10 seconds, then washed in hot water and dried.
 EMI25.3
 



  Another part of the fabric was treated at 15 ° C for 13 minutes, this treatment being further followed by washing in hot water and drying.



   With regard to flame resistance it was found that the qualities of the two samples were substantially the same and the respective finishes had substantially the same duration.
This example also indicates a way by which the fold of the solution can be ruled. externally, that is to say
 EMI25.4
 It also shows that by means of an aldehyde the product can be made resistant to swelling or stable in water.
 EMI25.5
 T.'t 1 ': w 10.



  We applied by the usual procedure, deorit above,
 EMI25.6
 a mixture containing 100 parts of dinyandiamide, 200 parts of phosphoric acid (75%), 100 parts of water, 15 parts of hy-
 EMI25.7
 Ammonium drozyde (28%) and 95 parts of formaldehyde (3 μm). The treatment was carried out at 165.0 for 5 minutes.



  Om. got the results desirca.



  This example beams the use of a different weak base

 <Desc / Clms Page number 26>

 
 EMI26.1
 the external r'2 "lage of the pi and the use of an aldelyde to increase the resll:! t ± 'nce au gOllfle;' ient.



  Here is yet another example of: elJL8 genre: EXE ". P12 11.



  E.:,y;lcyé, applying the process described above, a;, 1uh, .ge '30:, 1) 08, -, 300 parts of b1uret, 100 parts of phc5hcriqu8 acid (75% ), 150 parts of water, 5 parts of AWJ110uiura hydroxide (86%) and 25 parts of aldelyde for, ti, iue (37). The milking:; the.zt was carried out at 170 * 0 for 5 minutes.



  The above results were obtained.



  Here is an aortra example: lt employing the i oxide forming
 EMI26.2
 an acid:
 EMI26.3
 & ± 1, iLl there 'an 8J "I, loYf: Í. Applying the devouring process. Oo.pcse of 300 parts of urea, 100 parts of phC8 pentoxide} hore (P2Q5)' 2QQ parts of Water, 1C ± parts of atOniUlN hydroxide (28%) and 5C parts of formaldehyde (37%). The treatment was carried out at 15,590 for 10 minutes obtained the desired results.



  The e; ? .g le s x u lv at, 1 t ¯, lo; .. trent the edlplci of acids other than artophosrhortque acid. m (z .-- 2L'E 13.



  It employed, by applying the current process, one, ùélii, ie -.caç: s of 18Q parts of urea, 60 parts of tallow cric acid (cf'iã.), 50 parts of water, 15 parts of sodium hydroxide (26% ') and 50 parts of formaldehyde (57%).



  The treatment was et'- erectcol at 170 ° C for 6 minutes.



  0.1 got the desired results.



  % ìî9Jl 14 Qa applied a u: mixture oa.,. i cssed with 100 parts of acid ('rthrphoSI he r $ l! x,;. 100 parts of urn, 1CO parts of ac8taid and 100 parts of water on a tisDi) of cctcn, that we have s4oh,

 <Desc / Clms Page number 27>

 
 EMI27.1
 treated for 20 iuinutes z 14Q. 0, washed and s4ehe (and example shows the use of a weak base).



    We have quoted.! the desired results.



   EXEPLE 15
 EMI27.2
 A neelan6e was prepared containing 1qu parts of metaphosphorus acid, 800 parts of urea and? 0 parts of water, the method of application being the same as in the example, 1ple 'prlo- 1;.
 EMI27.3
 tooth. Processing has been completed. 170.This lasted 4 minutes. the desired results were obtained.



     EXAMPLE 16 A mixture of 300 parts of sulfuric acid was prepared
 EMI27.4
 So, sentrê and.de 90Q parts of urn: it was heated for 3 hours 82 C and allowed to stand for 24 hours. We have
 EMI27.5
 Sufficient hot water was added to obtain a clear solution, which was applied to a cotton fabric by the usual method.



   We obtained a fabric having good flame resistance
EXAMPLE 17
A solution was prepared by heating 180 parts of
 EMI27.6
 calcium phytate, 12C parts cY.:s11que, 250 parts of urea and 250 parts of forardet and then added 500 parts of water. The precipitate was filtered to separate it off. first of all calcium excalate, then the filtered account containing mainly phytic acid, urn and
 EMI27.7
 The amide was applied by impregnation to a cotton fabric which was then dried. The treatment was carried out at 155.0 and lasted 8 minutes, after which it was washed in water and dried.



   The fabric had good flame resistance.
 EMI27.8
 



  The following examples show: t 1 'e,; q- l c I mixed acids-

 <Desc / Clms Page number 28>

 
 EMI28.1
 xzdi> L'z 18
 EMI28.2
 We have e lr> .é, in 1) 1 a le lcocéda cCU1'atlt. an edition this year of 2üü parts of LR ..:. 6, of 50 parts of c.rthcphcshcri7: e acid (75), 50 parts of sulfuric acid (oone.), 100 parts of water, 15 parts of ammo hydroxide, luffi (28) and 50 parts of ald. :: r: wof fornic (37i). The treatment was carried out at 170 ° C and lasted 5; <; lnuta8.

   We got the results
 EMI28.3
 d if these
 EMI28.4
 : E; XE: c: 1'U 19 0, a I) prepared a l: éla.ye co.i, os: from 1UO parts of orthophoB acid [hcrigue (75%), 55 parts of nitric acid (cono.), 2'10 parts of urn and 100 parts of water, and it was applied on a cotton sheet by the prco << d6 described above, the treatment was carried out peridai-it 20 iaîiiutex 1>. 14U'J We got the dosed results.



  EX: E1.iI? L 20 Qn has prepared a: .1rHDlige cc, pcsé of 50 parts of pyrophesihoric acid, 50 parts of metaphicphric acid, 200 parts of acetate-aid and 15ex parts of water, the process of application 4ftaat le , lê! I that the one who dated described above, and treats it.:rent, which lasted 5 LUJ1t: tet>, having been performed at 1fi @ C.
 EMI28.5
 



  We got the desired results.
 EMI28.6
 As other examples of mixed weak bases, we
 EMI28.7
 will cite the following:
 EMI28.8
 i. ZXEI, '2L-Z 21 We have e.illc, 7', O, in appllqcaat the current procedure, a solution coapcsée of fies parts of diayandiamide, 75.0 parts of a <-; 6; ta-. .ide, 100 parts of acid j: 5 <roj; hosjhorigue and 2 <1.Q parts of water. The tr.ite.ae..t was carried out at 160 ° C and lasted 5 minutes.



  Where obtained the desired results *

 <Desc / Clms Page number 29>

 
 EMI29.1
 xxx1oL3 33.
 EMI29.2
 Prepared a mixed mixture of 132 parts of urea, 8 parts of mOlA5iLie, 66 parts of phosghete di am: i10niq ue and 150 parts of water and applied it to a cotton wool in the usual way, the treatment being carried out at 168 c for 3 minutes.



   The desired results were obtained.
 EMI29.3
 



  A mixture of 35 parts urea, 1 parts ovana-aaatamide, 50 parts orthophosphoric acid (75%) and 165 parts water was prepared. It was applied to cotton cloth and obtained the desired results. the treatment having been carried out at 155 ° C. and having lasted 5 minutes.
 EMI29.4
 By repeating this operation without the eyano-aoetaraide, an excessive softening was obtained.
Here are some examples of the use of base salts *
 EMI29.5
 EX1i: IIE 24.



  A mixture of 160 parts of bicarboa te-amidoguanidine, OO parts of urea, 150 parts of orthaphospharic acid (75%) and 500 parts of water was prepared. The operation was carried out as usual, the treatment at 177 ° C. having lasted 4 minutes.
 EMI29.6
 cy, obtained the desired results = ,. M * there t5.



  A dosage of 61 parts of serni-earpazide hydrochloride, 45 parts of guanidin carbOfate, 45 parts of oyano-aoetamide was prepared. 35 parts of urea, 50 parts of orthphosphoric acid (75%) and 60 parts of water and applied by the usual method, the hundred treatment having been carried out at 168 ° C and having lasted 4 minutes.



  (aa obtained the key results.



  Here are some more examples of the use of

 <Desc / Clms Page number 30>

 
 EMI30.1
 fixed ... bases, exe .I1;.: 'z dt: rs which one e1l [101st a 00 "; 6 she is afraid (C.1Serve' the t.axi; rr:" has resistance, and one or plL 'If the basis is weak, day to day ensure an act, 1on of arnortisse- ze: it and adjustment of the reaction.



  2x-z., "PLU 6.



  We have ,,, rlcyu, proceeding oonnie usually, a co .posed solution of 100 parts of urea, 100 parts of carbonate dāai: o-guanidina, 1C; J parts of arthophosphic acid (' 75jvj, 100 parts of water, 15 parts of aul hydroxide, j1onluill (88%) and 50 parts of fermic aldehyde (3? Jo), The treat #, lt was carried out L 17CC and a dirs 5 minutes. to a cbteuu the results of sir.:s, E1l'L: E '7.



  We prepared a: Jl \ la,: ge co.: DanemarkPCS of 50 parts of dicyan- dia ;, ilde, 113 parts of ur, e, 10.5 parts of guaaidin carbonate, 75 parts of phosphoric acid (75%) and 158 parts water. It was applied to a cotton fabric by the usual preceding lFt, the treatmentL, 6: Jt ûta ,, t carried out at 170C little 10.; At> iL = tes, 0n obtained a very durable resistance io. la! la -: le - EXSMPL-E 28.



  A short mixture of 57 parts of polypyrcphosphic acid, 66 parts of guanidine carbcaate,
 EMI30.2
 132 parts of urea and 255 parts of water, and we applied it
 EMI30.3
 by the: prQoddtb ', ;;. uel, treats: .eit having uta effected at 165'C i and having hard 5, ni, autes. We obtained, on a cotton fabric, an exeellA: .te r. ', Sistan-0 la: f1a.L, ua and an excellent dec roe, EX "5: #LE 29.



  Or has prepared U1; a <la:> je eo..pc x, of 40 parts of guanylur06 eulfate, 81 parts of: rea, 53 parts of crthophcsrhoric acid (75%) and 90 parts of water, and Qn applied it to a cloth of cctcn by the usual priest, by treating it

 <Desc / Clms Page number 31>

   160 * 0 for 5 minutes.
 EMI31.1
 



  We obtained a very resistant bucket, the fla, 2: 1e.



  EXE]. {±> L1i: 30.



  A mixture consisting of 3 parts of urea, 160 parts of amincguanidine bicarbonate, 150 parts of phosphorus pentoxide (75%) and 500 parts of water was prepared.
 EMI31.2
 applied on a cotton fabric by the prore. d; usual and obtained a fabric having a very good resistance to. The treatment was carried out at 170 ° C and lasted <5 minutes.



   Here are examples of using a weak base to partially produce an energetic base '
 EMI31.3
 EXE:. 'Z'T., E 31.



  65.0 parts of dieyand3a! Nide, 10Q parts of orthophosyhoric aid (75%) and 100 parts of water were heated at T4G, a violent reaction taking place and the temperature increasing. Under these conditions a useful quantity is formed. notable guanylurea. To this amount, 150 parts time and 110 parts of water were added and the solution thus obtained was applied to a cotton cloth, which was then dried, then treated at 170 ° C. for 5 minutes, washed and dried.



   Excellent and durable strength was obtained,
 EMI31.4
 f1f'1 airae EXAMPLE 32.



  A, 953, 4 parts of dicyandiamirl, 168 parts of di-ionic hydrogen orthophosphate were heated in a covered container; in these solutions a substantial amount of guanidine was formed in the form of guanidine phosphate. 24 parts of this material were mixed with 150 parts of hot water and the solution thus obtained was applied.
 EMI31.5
 on a cotton cloth by the usual procedure. Good results have been obtained. The following examples show the use of

 <Desc / Clms Page number 32>

 
 EMI32.1
 base substitution
 EMI32.2
 EXE # u :: 33.



  We have prepared a mixture of 65 parts of dicyandiauid, 1GO ructies of crthcphoshoric acid (75), 150 parts of created, 28 parts of, phsnylbigLJ8üidin and 210 parts of water and c ;, a applied by the usual procedure. To obtained a bo "ue r-sistal.ce la fla: e 3XE: .TLE 34.



  A mixture of 50 parts of dicya :, - dianide, 12Q parts of: ethylurea, 10 parts of glycine carbonate, 75 parts of crthophoslhoric acid (75%) and 400 parts was prepared. of water- 4n applied the; r,.: aa..ge on a tissue of octcn by the 1-rcr - of usual and obtained a product i.i & 1 resistant to flaaEie- Here are examples of th ':. use of 8ukstitvés acids, E'd3-.h 35.



  Cn was emplcya, applying the method described, an r: l, .18.l: e oa.:piece of 204 'parts of urea, 100 parts of acid sul! A: .Ücp, e. 1GK? parts of water, 15 parts of α-hydroxide: J. "o-niu, (J8j &) and 50 parts of formaldehyde (3%).



  We have obtained!) 'The results of ... if rÓs,% 3àbLl 36.



  An ec..aics4 of 150 parts urs, 10 parts artaonium hexaphsphate dinitride and 350 parts 8L water was applied; a tissue of crto, -, qU'Cf ! dried, treated at 160.C 17 7; r.i, ut, es, then washed and dried.



  Op has obtained u.e bc, .ne resistance9., '"Ee lasting the flc.:..le ..



  EXE1 # L 37.



  We repaired a mixture in ch: .tLl.aLlt first at 8 & .c pe.¯dD, t u .-. E hour 30C parts of GL acid: lfüt'iCj, ue, 300 parts of urn and 1CG parts of water. He made himself a zains syrup, which he then diluted with WQ parts of water. We have lnpregn4

 <Desc / Clms Page number 33>

 
 EMI33.1
 a fabric of ccta l, that the en a srahd, t rai té, lO'1é and t 's ..; key as in the xesples -preédel1ts.



  The fabric had good ion resistance.
 EMI33.2
 



  C7 ', L.n.1 38.



  Oh reacted 140 parts of phosphorous pentoxide and z parts of ar carbonate: unon1vm can form diasidophosphoric acid, to which is added 3gag parts of urea, 195 parts of guinidin carbonate 65U left. of water.



  ; !. ' applied this mixture to a tis ad de aotan by the usual procedure.



   We got good results
The above formulas have all been applied to
 EMI33.3
 a material this Il! Jlosique based on cotton., Example: The following Jljle shows the application of this process to wood pulp.



   EXAMPLE 39.
 EMI33.4
 



  We soaked wood pulx in sheets, like the one we use for the manufacture of viscose, in pyro
 EMI33.5
 a hot solution of 57 parts of POljfphosJ, ho, riqu6 acid.



  66 parts of urea and 350 parts of water, then 0.1 squeezed it thoroughly, dried and treated at 17000 for 6-1 # utes. The pulp thus obtained had the appearance of ordinary pulp and was extrej-nersat resistant to flatl: The following example shows the application s. trieots, downy, very acr.bustilles rayon fabrics L 1J: X "NDE? LE 40.



    A mixture of 33 parts of dicyan-
 EMI33.6
 dianide, 1 <3Q parts duration, 50 crthcphcsrhoric acid (75%), 10 parts of c8rbc; guanidine iate and 5GG parts of water, and it was applied to the rayon fabric of the type mentioned above, by the usual procedure, the treatment being carried out at 170 ° C. and for 6 minutes.
The knitted fabric thus treated had good strength

 <Desc / Clms Page number 34>

 
 EMI34.1
 at the [1r. ,,the -
 EMI34.2
 Vcl? I application examples dL concedes a. tissues 1 base of .cteine.



  2XE.LE 41. a repairs a.:., Cc -pc mixture of 116 parts of carbon dioxide, 289 parts of urea, 162 parts of acid
 EMI34.3
 at
 EMI34.4
 crthcç, hci, 1, rriu <: e (75) and 433 parts of water. We / apply this on the wool fabric L 1ilµ / à, which we Suché, treated pe dilnt 5 5 .i, u tes at 17000, washed and dried.



  , g aiiisi woolen fabric treated uiie bcw.ie resisted, -. ce the flD,:.:; e 'EX'S..1! 42.



  We have r, -. P etj oe of honey 'recedes, zains in replacing the wool by a ti ssu of saie tussah iL 1QC> -'
 EMI34.5
 The fabric thus treated had a bucket resistance to
 EMI34.6
 The la e.



  E1: THE 43.



  We apr: pa rb un.: Néla .ge (te dl'C;, .-, 33 parts of dioyaü- diaJ.1ide, 1CO parts of urn, 10 parts of carbc:, ate of guaüidirl6, 50 parts crthcphosphoï'iqua 'acid (75%) and 400 parts water, and applied it to a fabric containing 75% tilde rayon and S5 / o aralac, by the usual procedure, treated it; slow both performed at 1550 * C and for 4 minutes.
 EMI34.7
 



  The fabric thus treated: had a bucket resistance to
 EMI34.8
 flre;. 113 '
 EMI34.9
 
 EMI34.10
 The following axes '1f, es ii (, i-itreit e;' 1floi of energy bases only 2X3L2 44.



  C? 31 to e.iploy, by applying the prc, 3, usual edt, a sclutian oc: pcse of 100 parts of aminaguaai8ine carbonate, 50 parts of phcsrhori> 1,: ue (75%), 8Q parts water, 25 parts a'a hydroxide; c <, iuiù ($ 26), 80 parts water and

 <Desc / Clms Page number 35>

 
 EMI35.1
 25 parts of fcr :: ic aldehyde (.57%) The treatment was carried out at 15540 and lasted 12 minutes. A good flame resistance was obtained.
EXAMPLE 45.
 EMI35.2
 



  An oamyose mixture of 6Q parts of pyrophosphoric acid, 320 parts of guanidine carbonate and:
 EMI35.3
 750 parts of eaa, and it was applied .., to a tissue of (ctQ1 by the usual procedure, the treatment being carried out at. 1q ('C and for 5 minutes - The tissue had' Une 'bo: , not flame resistant, but little solidity
 EMI35.4
 Examples Bt! .1 are examples of using strong bases and weak bases, which are not in the form of salts. EXAMPLE 46.
 EMI35.5
 



  (4In prepared a half-based mixture of 50 parts of didydiamide, 115 parts of urea, 75 parts of phosphoric acid and 175 parts of an aqueous solution containing 5.1
 EMI35.6
 parts of guanidine, and applied to a weave of o # tQii by the usual method. The treated lasted 5 minutes and
 EMI35.7
 the temperature was 165 ° C.



  Very durable resistance to. fla. 111, EXAMPLE 47.



  We. prepared a z: éla, ige oori, csé of 85 parts of urea.



  53 parts of orthphosphoric acid (75%) and 100 parts of an aqueous solutiol containing 210 parts of guanylurea, and applied to cotton in the usual manner. The duration of the treatment was 4 minutes and the temperature was 165 C.
 EMI35.8
 



  Qn got u.e very bc, did not resist (1ce & la fl amioe
Applicants have also obtained good results on paper and wood with this precedent. In this case, especially when it comes to wood, it is necessary to use s. the employment of a

 <Desc / Clms Page number 36>

 
 EMI36.1
 pressure for pp11'-1 uel 'sclLtion, or else Oh can use u :. treated.¯e., ti ar the empty fear; li .4ne the air, this treatment being followed by the application of the solution under pressure, after removing the excess, drying, if desired, and we treat.



   It has also been found that the method is applicable to
 EMI36.2
 treatment of organic materials such as carbohydrates and dyes belonging to OR groups or groups 1; .II and capable of separating with reactive acids, provided that these materials do not excessively volatile or altered in an undesirable manner under the conditions of the procedure
Excellent results are obtained with regard to
 EMI36.3
 both the hard and the 1 '"Sistl; ldce when the cellulose fibers made resistant to the by this process by means of rigid phosphoric acid ccut a group of phosphoric acid for each group of four units of pyrance contained in
 EMI36.4
 cellulose.

   The fact that puddle resistance can be achieved with such a small combination is remarkable and
 EMI36.5
 The authors believe that it is due to almost all of the ingredients of the complex applied to the fibrous material to help to reduce the swelling. Thus, the complexes which produce resistance to flame contain large amounts of nitrogen and phosphorus, both of which produce, and burn, 0-a or volatile matter which tends to con-
 EMI36.6
 to .. Deny oxygen and stifle the f1L1J [I.

   When the ratio between the grcup "of the acid and the uúft,; s of pyrancse dLnil: U8. The rdsistBr> ce It la flaLJ:, 1e decreases by as much Some zatiérel dice indicated above ensure a r -SiSt8 .. () 6 Lwsit) e the action of salt and to an energetic soap'.age, which makes the prcduit fi., I particularly useful for making the ulifcr :: 16s iiilitaires which feel prone to be submitted it.

 <Desc / Clms Page number 37>

 
 EMI37.1
 savannages and extreme handling, zergic.

   In many examples in the douais, the final product has a more pronounced capacity for ion exchange than in other examples, the active groups of the anions present in the complex. having a certain affinity for cations like those
 EMI37.2
 which are present in salt water, the solutions co {"> ntrf ;:

  \ .es of soap and hard water .. As a result of this ion exchange capacity the characteristics of resistance to ,, the
 EMI37.3
 flame sometimes slightly decrease in salt water pra, nce and under the action of vigorous soaping, although the product
 EMI37.4
 either relatively resistant to water, dry cleaning and ordinary washing
 EMI37.5
 It has also been agreed that the fabrics treated with the subject prooeae have good resistance to wrinkling and creasing. especially when the higher degrees of substitution are used in cellulose * Although the fabrics treated with this
 EMI37.6
 proceeded to have a certain tel1dance to.

   swell in the presence of water, they yield water easily and dry quickly. This property of rapid drying is markedly in contrast to
 EMI37.7
 the way the same fabrics behave when they have not been treated, because when these untreated fabrics absorb water * it evaporates slowly ;;
Applicants believe that the reduction in flame resistance, a reduction caused by metal ions, is
 EMI37.8
 due in the first place to the reJrq;

  > laceIlleat the value nitrogen by the metal and secondly to the fact that 1 addition of the ion
 EMI37.9
 The metal to the phosphate radical reduces the ease of conversion of this group into oxides of phosphorus which are so valuable, to prevent loitering '
 EMI37.10
 with regard to the resistance to 7'é.aha "ge of the ions and, in addition, as had been said, the improvement of the duration in spite of the action of the saline solutions and the soap solutions;

 <Desc / Clms Page number 38>

 
 EMI38.1
 we had to obtain them with the d, The: a of the solidity of the tissue by increasing lCre., and the duration of the treatment e:; t, for example made: last the treatment..t e..vircn 30 minutes instead of 'about.:. inrtes, and raising the temperature to about 15000 to e -virca 175' G, then washing in hot water and knowing.

   Applicants prefer 4, ent oc ,, isolate and retain c3di asire., - ent of approximately 80; at about 90 days of the resistance to the treatment, although some may drop lower (a reduction of .5 (ô on the value of the is L about the maxium that can be reached), and they thus obtain a longer duration 1ci, zue with the solution and the tissue type nose.



  We can also obtain the resistance Y the exchange of icons, and by obtaining it from r.jf <'ence, when the resistance of the tissues is bc, ae cu excellent, au.; Ioyen of groups of act which eyéahe: .t or delay the addition of metal ions. The groups of a ..: .. tQuiac, parex, ftple, smell re-ilplauis very easily by a metallic ion, while the groups such as guanylurea, guanidine, biguani4lae, etc. are rerplack; s easily fjcins.

   In consuenoe, the -L'or. in which these nhimiquos products are used in sufficient quantities ensures a segregated resistance to the exchange of icns and a duration all the more la, igue despite
 EMI38.2
 the action of soaping and leaching- As we said above, some of the basics'
 EMI38.3
 of these lexes are created during the reaction in solution and followed; , the tissue during treatment. This is not true when using salts closed by acid and nitrogen, such as: ammonium phosphate and ammonium phosphate, zi..s t .Hydrazine phosphate,
 EMI38.4
 although there are changes and an evolution towards
 EMI38.5
 more coiaplexes of nitrogen, where free phcs1hariG.ue acid is used as dildiet material.



  What has just been said in rc, the place is due until

 <Desc / Clms Page number 39>

 point to the fact that when phosphoric acid
 EMI39.1
 is heated to a high temperature with nitrogen acids, ammonia is liberated and acts against the ammonia which otherwise is supplied by the ammonium phosphate. The ease with which these complex compounds force each other depends
 EMI39.2
 also to a certain extent of the azctâ couipose used in. the origin. For example, dicyandiamide is a very serious acne.
 EMI39.3
 reactive under these conditions and reacts with phophoric acid or ammonium phosphate to form more complex substances ensuring a longer life for the finished product.



   In the examples given, it is often desirable to heat the solution during its preparation.
 EMI39.4
 tion, with a view to perl # ttre to some of these chai2-, e, neritsde to occur. For example, in a fae ,, iule (} Cl! 1prenailt the use of dic; andiamfde, phosphoric acid, urea and water, one can first react the diayandiamide with the acid and a little to The water at high temperatures, after which urea and the remainder of the water are added to form the utiofinal.



     The exchange of ions can be reduced to a certain point: pointa by subsequent treatments using materials
 EMI39.5
 such as the eC1'J) dared to nitrogen which are identified above, but it seems that little is gained by this way of proceeding.
In general, for the application of the procedure, the temperature
 EMI39.6
 Preferably, the treatment time varies between oi.viton 140.0 and around R45C, and the treatment time varies between around 45 minutes and around 1/2 minute.
 EMI39.7
 results,

  Applicants claimed a temperature varying between 160 ° C. and 180 ° C. and a treatment time varying between 15 and 3 minutes. These figures are valid for the typical apparatus. When the equipment is large enough and
 EMI39.8
 allows to process the material fast enough ITf7nt for the bescins

 <Desc / Clms Page number 40>

 
 EMI40.1
 of OOL., E oce, the te .1) uratu it can be lower and the hardening of the draft.;. is longer, as has already been said above ..



  The s, -ol.1D.ge and the pel: \ 1E 'treatment, "t be cOI, bL1S in one cperatioi, all thus obtaining the desired treatment.



  Dar.s le t'su, J. (1, le; [, and "avide" is used in the sense using utiic reliance on energetic acids assuring the finite resistance and able to act on cellulose and on the ac., i.pcaé nitrogenous under the conditions of the operation -, as was said above, these acids not being excessively volatile and neither did not produce, during the operation, of
 EMI40.2
 : prC'duitchi.Liues capable of del-1t, detrimental to the nature of the fibers:

     it is also used in the sense of the equivalents of these acids, as indicated in the description. The mct "base" applies only to gold bases.
 EMI40.3
 Nitrogen-containing ganics, whether weak, strong or amphatic, soluble in water at the mine up to a certain level, capable, under the conditions of the operation,
 EMI40.4
 to reduce the acidity and to dampen, :: cd ..: Nr the reaction enters the cellulose and the acid and entering the aeid-cellulcse complex by providing nitrogen to this complex and data which the content carbon is not large enough to reduce the inflam ::; ability in a detrimental way: it is also aimed at equivalents, as indicated in the description.



   It is a material of this kind that must be used following
 EMI40.5
 the 1) rÀise, -tp 1 ;; Ye <, t] on, This does not mean, however, that one cannot use in: 1 ęaie another basic material or other ingredients as dàaààitions, as long as there is no disturbance in the desired reactions and in the final result-
 EMI40.6
 Thus, rar exeitle, one can use energetic bases

 <Desc / Clms Page number 41>

 for adjusting the pH, provided that the base material of the present invention is also employed, which material will provide nitrogen
 EMI41.1
 complex.When a strong base is used to regulate the pH,

  a weak base must be employed at the same time. among the energetic bases which can be employed to regulate the pHon men-
 EMI41.2
 will work the alethvin triamine, triethandiamine.lthydro- sium.
 EMI41.3
 sodium xide, sodium carbonate and potassium hydroxide Jjioqtttoioi we have. in view / finished flame resistant profiaits. As said above, when it is desired to obtain flame resistance and at the same time. resistance to action
 EMI41.4
 moisture, there should be g * on the finished fabric, from 1 to bl. from le.

   the basic element of the acid (on% "6ase of the use of phosphoric acid) and from 0.25 to 6% nitrogen. When the resistance to the action of
 EMI41.5
 1 * h = id.ity is the result sought in the first place, the percentage of base isolation of acid and nitrogen on the finished fabric substantially
 EMI41.6
 can be / reduced as small amounts will work. In general, it is the acid groups which give resistance to the action of humidity. However, some of the bases, such as pheno-guanidinate, for example, help to give resistance to the action of humidity.

   The acid must be damped. With regard to resistance to the action of humidity, applicants have found, based on the use of phosphoric acid, which is obtained, very good results. with 1 group of phosphoric acid for 8 units of pyranose. A proportion down to 1 to 16 further improves the original tissue.



   While the incandescent persists for an appreciable period of time on the fabrics treated by the present methods intended to protect against the flame, on the fabrics treated by the process of the invention, the incandescence almost disappears. immediately as soon as the test sample is removed from the flame.
 EMI41.7
 



  ] Reference will now be made to the engagement of aldehydes when it is desired to reduce the swelling of the tissue subjected to the continuous action of

 <Desc / Clms Page number 42>

 humidity, the products used being, by way of example, formic aldehyde and ortophosphoric acid; the amount of formaldehyde generally varies between about 0.2 gram mole and 1.5 gram mole per 1 gram mole of orthophosphoric acid, the preferred amount varying between 0.4 gram mole and 1.0; 0 gram-molecule of aldehyde forms per 1 gram-molecule of phosphorous acid.

   If the amount of aldehyde is very close to the lower limit, care should be taken to reduce the damping action during processing. If too much aldehyde is added, the action of damping is too strong and the treatment should last a long time.



  Here are still further examples of the use of aldehydes.



   EXAMPLE 48.



   A solution was prepared as described in Example
9, this solution being composed of 100 parts of urea, 50 parts of orthophosphoric acid (75%), 7 parts of ammonium hydroxide (28%), 50 parts of formaldehyde (37 %) and of
50 parts of water.



   The solution was clear and a cotton twill was further impregnated as described in Example 9, followed by ream drying as described.



   Part of the fabric was treated at 172-173 C for 3 minutes and 40 seconds, after which it was also washed in hot water and dried.



   Another part of the fabric was treated at 150 ° C for 22 minutes after which it was also washed in hot water and dried.



   The two samples had substantially the same flame resistance and the end product life was also substantially the same.

 <Desc / Clms Page number 43>

 



  The essential difference between the two solutions of
 EMI43.1
 Examples 9 and 48, was that an used, in Ex6DJrle 48, 50 parts of a1déd. formic instead of 10 in the formula of Example 9. This increase in the amount of formaldehyde increases the time required for the treatment.
 EMI43.2
 



  It should be noted 6ge.ler # nt that, .. as the processing capacity increased, the time required for processing decreased, and rioiproquemen-b JJ: XEJ! #LE 49 <... .



  A solution was prepared as prOl3éd.emrlleJ1t, but this solution was composed of 100 parts urea, 50 parts 'orthophosphoric acid' (74%). of? parts of ammonium hydroxide (218), 27 parts of formaldehyde (37%) and 55 parts of water.



   The solution, which was clear, was applied to a cotton cloth, which was rowed dry as described in the other examples * '
 EMI43.3
 The fabric was then treated z, 130 * 0 for 2 hours, then washed and dried as usual. It was found that the fabric thus treated was flame resistant and that the
 EMI43.4
 qualiti3a resistance st. the flame and duration of the final product were / fully satisfactory.



   This example also shows that when the temperature
 EMI43.5
 treatment decreases the duration of the treite: nel1t said to be longer In: 1? LE 50.
 EMI43.6
 



  In this example the 3rd formula was used and the same procedure as in the example pr4obderzt, but in this case the cotton tissue was treated at a te: ljpüratlire of 205 * 0 for 30 seconds, harsh. It was washed and dried as usual '
The end product was both satisfying and durable.

 <Desc / Clms Page number 44>

 



  Aldehydes other than aldehyde can be used
 EMI44.1
 formic'iPar eX0ül} le, a sclution composed of 200 parts of urn, 10 <J parts of phosphoric acid (75%), 114 parts of water, 15 parts of asOfjium hydroxide (28j) and 50 parts of glycxal (30%) gives good results * As another example. aldehyde can be used instead of fornic aldehyde A solution composed of 200 parts of urn, 100 parts of phosphoric acid (75%), 114 parts of water, 15 parts of ammc hydroxide
 EMI44.2
 nium (38%) and 75 parts of chloral hydrate gives bc.4s r..sLltats.



  Applicants have also employed mixtures of aldehydes.
 EMI44.3
 



  : For example, a solution composed of 800 parts of ur4e, 100 parts of Qrthophosihoric acid (75%), 100 parts of water, 15 parts of ammonium hydroxide (28%), 25 per - Ties of formaldehyde (37%) and 25 parts of glyoxal (30%) gives good results.



   Qn can use other aldehydes such as, for
 EMI44.4
 exeurle. aaetiguo aldehyde, saralf3ne and aldol. Zdaldhydne should have a low r ,, 4olcular weight (a carbon chain of 1-4), react with the cc., Which contains azccte and it is desirable that it also react with cellulose in the cells. conditions of the operation.



     The invention not only conceives of the foregoing methods but also as new industrial products.
 EMI44.5
 fibrous materials QQnforr; es to. those obtained by these processes
CLAIMS.
 EMI44.6
 



  1. A method of rendering flame resistant a fibrous material of the type composed of cellulosic substances based on protein or analogous organic substances and mixtures thereof, or of rendering resistant to the action of
 EMI44.7
 moisture, a pellulosic material or a fibrous material

 <Desc / Clms Page number 45>

   analogous organic, characterized in that it consists of. subject matter to Inaction of a solution
 EMI45.1
 aqueous solution of energetic acid ensuring the resJ.stf1ac $ to the flame of a vigorous aid ensuring resistance to the action of humidity, and of a soluble organic base containing nitrogen, to dry the material. at. heat it up to a temperature and for a period of time both having the effect of producing Qo:

  chemical nbtl18.ieons with; matter, to introduce groups of acid and dice; 1 the ate in the complex, then washing the treated material, drying it, the acid
 EMI45.2
 with the acid and the base being present in:, n the solution in sufficient quantity to produce a resistance, noticeable to the action of humidity or to. ia fla: soul, and the pH of the soelutian being such that that of the material treated has a value varying substantially between 2 and 7.
 EMI45.3
 



  2. Method according to claim 1, in which the base is a weak base or a strong base or a mixture of one or more weak bases with one or more bases.
 EMI45.4
 .nerg1t !, ea. 3t'Broedé according to claim 1, wherein the base and / or acid are employed in the form of a salt.



     4. A method according to claim 1, wherein the base is urea or guanidine or a mixture of urea and guanidine.



   5. A process according to claim 1, wherein the base is a mixture of urea and guadidine carbonate. 6. A process according to claim 1, wherein the base is guanylurea.



   7. The method of claim 1, wherein
 EMI45.5
 the acid is orthophGsphori acid (EU-8. A process according to claim 1, wherein
 EMI45.6
 the amide is employed in the form of hydrogenated diammonium phosphate.

 <Desc / Clms Page number 46>

 
 EMI46.1
 



  9. proceed according to reveiidication 1, in which the acid is solfonic or sulfuric acid.



   10. The method of claim 1, wherein the acid is a substituted acid.



   11. The method of claim 1, wherein the concentration of sclidic material in the solution ranges from about 30 to about 50%.
 EMI46.2
 



  13. 1? Rock "d <: according to one or other of the preceding claims, said that the proportions of acid and base are such as to introduce into the final product in-
 EMI46.3
 viran Q, 5 to about 5% of the 610, acid base based on the use of orthophosl, hcric acid in the solution for comparison, and about 8.85 or so azata 13. The method of claim 1, wherein
 EMI46.4
 the acid is e, a1'Iay. under the form of ammonium phosphate and the base is dioyanamide.



   14. The method of claim 1, wherein the
 EMI46.5
 solution contains the product of the reaction of the acid and the base.
15. The method of claim 13 wherein the solution is applied hot.
16. The method according to either of the preceding claims, wherein the treatment temperature varies substantially between 137 C and 205 C and the duration of the treatment, substantially between 120 minutes and 30 seccndes @.



   17, Preceding claim 1, wherein the
 EMI46.6
 rsigbaD0e the action of Ilhu8iàit is given # the fibrous cellulosic material by subjecting this material to the action of an aqueous solution of a strong acid ensuring the re-
 EMI46.7
 sjsta, ice 1; the action. of hu: .1idit \ #, in the presence of an agent of a;,> urtîsxe., ic. ,, t, drying it and treating it by the action of heat to produce a chemical combination notable

 <Desc / Clms Page number 47>

 between acid and cellulose.



   18. A method according to any one of the preceding claims, 'wherein the solution contains an aldehyde such as formaldehyde, to reduce the swelling in the water of the material so treated.
19. A method for rendering flame resistant, according to claim 1, wherein the treatment temperature varies substantially from 160 C to 182 C and the duration of the treatment from 15 minutes to 3 minutes.
20. The method of rendering flame resistant according to claim 1, wherein the processing temperature varies substantially from 120 C to 205 C and the processing time ranges from about 120 quests to about 30 seconds.