DE1720175A1 - Phosphorus containing fire retardant cellulosic compositions - Google Patents

Description

172017S-

Patent attorneys Dipl-Ing. RVeickmann, Dr. Ing.A. Weickmann

Dipl.-Ing. H. Weickmann, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber

8 MUNICH 27, DEN

MÖHLSTRASSE 22, CALL NUMBER 48 3921/22

Casa Kr. 67

tf _e p ₄ Stsvans Ba öo _Q Ine «^ (S-arfield, ITm * Jei» a © 3r ₉ USA

e ₉

cölliiloeehaltigö

present Srfindimg concerns phosplioren-felialtende, isnda calluloeehaltigo SusaMaeriaetsnELgen *. Xnslisepnclsre refers to the invention of both as well as nitrogen-containing Oellulossy around them

lot Ot) Ib hangern got that cellulose, especially in Voxm. öiaöx · lia

by treatment with phosphorus containing on & mi wia example white phoopioric acid ©, or with ¥ ör «- * Oiniim \ g®n _t ^ i® when burning Pliosphoreäura su are able to form _β fousrlieiamonda own account varlishen v / e are ^ e ^ ioch ira "general as a result of the death Abbans dor CölluJ.000 oo.vriö -öinos?

1098237 1.9 OB

BATH ORiGfMAL

More recently, various treatment methods have been tried using pAOSphororganic compounds were used, the aim of these treatments was the generation feuerliemmsuder properties »without having any at the same time Destruction of the cellulose takes place. In carrying out these experiments, attention was also paid to this; that the phosphorus-containing agent is not removed in washing. In some cases nitrogen-containing organic compounds were found used to make the phosphorus compound insoluble and to see the effect of the phosphorus compounds on the physical body Modify properties of cellulose.

If today a number of different treatments are carried out in technical standards "then yet has none of these methods in terms of results produced fire-retardant properties" to a deterioration of the substrate proper "Community @ n _f on the type of application and in view of the costs to be acceptable It has been proven that the phosphorus content of most organophosphorus compounds is low, and in general it is no more than about 10 to about 15 parts by weight. Therefore, the organic compound must be added in a large amount in order to provide a sufficient amount of phosphorus, which is necessary to achieve the fire-retardant properties. The mechanics see properties of cellulose, especially in the form of a social structure, to a greater extent through increasing amounts of added

109823/1905

■ - 3 ~
ι

Chemicals adversely "are affected, it -was only a few so far engswendetsn treatments succeeded _s both a anziahmbarsn degree of feuerhasjiaenden properties than mechanical also not deteriorated char acteristics to achieve" SarübsrMnaus are most organophosphorus compounds expensive and ordinary applicators difficult to handle lo "b © n _s so that for this reason, too, the hitherto known treatments for establishing fire-resistant properties are subject to restrictions *

has now proven to be a synergistic effect between organic nitrogen and organic, nonionic Phosphorus with a view to imparting fire properties in cellulose there is «especially vmrde

obtained the knowledge that a reverse Besiehimg swischen nitrogen IMD phosphorus to achieve a given G-wheel on feuerheuaiaenden properties is "by replacing a leils of phosphorus contained in a feuerheimaend solubilizing Zusamaensetaung by nitrogen can maintain the gev ^ inschten f your retardant properties and equilateral some of the disadvantages of the previously known methods of treatment are reduced to a minimum.

are the most organic nitrogen compounds less expensive than the organophosphorus compounds and ia Ordinary systems easier to handle asu «In addition, own

109823/1905

many organic nitrogen compounds relatively high nitrogen contents " By replacing an organophosphorus compound with a low phosphorus content by a nitrogen organism Compound with a high nitrogen content can therefore lead to the Irsiöluag i'euerhessmender properties required substance amount can be reduced, whereby at the same time the adverse effects on the physical properties of the cellulose be reduced without affecting the fire-retardant properties » shafts are deteriorated.

JDio systematic development feuerhemraender additives, especially © · = · eondere for Celluloses has designed calibration difficult insofar warden achieved as a great influence of the substrate on the extent of feuerhemaiendsn properties "with a respective agent used in a gage surrounded amount was found. ₈ This influence is evident both in the molecular and in the macroscopic range · Certain molecular forms of cellulose, for example rayon "are more flammable than others! Forms, such as bainwool" In a similar way, certain physical "photomqh, for example lasers or yarns, are more flammable than other Formoa, for example fabrics woven from the same fibers or remotely woven. Furthermore, density or surface area per unit weight affects flammability, with light fabrics (134 g / m {4 ounces per square yard}) being more flammable than heavier fabrics Fabric, for example fabric with a weight of 268 g / m (8 ounces per square yard),

109823/1 90S

■ ■. . -.5 which have been woven from the same thread or yarn «

Zusätslich su this difficulty exists as yet Its.in (Seat of determining the fire retardant! "Properties. There is not even ein® generally accepted definition of ^B £ @ uerhemmden properties. ¹¹ In most cases, the sru. Test object is under the actual or simulated conditions * as they occur in the intended use, so that the standard of the properties is only related to the respective intended use fire retardant when applied to any form of cellulose is difficult, if not impossible »

In the present application, the term "fire-retardant" is used synonymously with the term ⁿ self- ^{releasing n} * This means that fire-retardant properties can be present, although the surface or the article in direct contact with an amine can burn ₉ where j ado oh the flame on the surface of the blessing taxide goes out when the flame source becomes antienit. So there is no spread of the fire. A reading that is used in the usual way to determine the fire he "imendan Mg.enschaftera in this sense is the so-called ver"

109823/1905

Tiksle Ilammentest, which is generally only on flat cellulose * forms is applicable, for example to cellulose fabric, and swar regardless of whether it is nonwovens, knitted or woven goods. In addition, it can be stuck on sheets of paper and the like can be applied. In this test, a fixed flame source is placed on the lower edge of a vertically suspended strip of material for a given period of time.

^ span directed and subsequently removed. The length of the charred or burnt rope, ie the "charring length" of the sample, is then measured and gives an indication of the fiery properties. On the other hand, the fire-retardant properties of wood that has been treated to reduce the flameability are often measured using the "crib" test (ASiM E 160-50) 24 test pieces with a length of 12.7 x 12.7 x 76 mm (1/2 " χ 1/2" χ 3 ^M ) for a period of 3 minutes of exposure to a flame with a temperature

P temperature of 315 - 3 ⁰ C are exposed. The weight loss (in %>) and the duration of the glow are then noted. Other teats have been developed for other forms of oilulose.

However 1st not only the Besiehung between feuerhemmsnden properties of various forms of cellulose due to the different test methods used difficult but there are aiioh just some of the previously applied Sestmethoden Dassu _p mil in Inägo; for each desired degree of accuracy the relative

109823/1905

Äiisras.80 to determine the fire-rhezamidal properties that are obtained by am * © ndtmg of two different treatment methods on the same substrate, "For example, the vertical © Plesmenteet is a relatively high measure for the fire-retardant properties" It was generally established that the If ¥ © RKO! xli3ngsl & ng © either less than about half dor Prob® or all Prob © is consumed * therefore, for example, a sample τ with ßinsr dimension of 254 or 304-, 62 ma {10 or 12 inch χ 2 1 / 2 inch) is used »then the properties are generally considered to be adequate, waxm the carbonization length less than a freely chosen value, which is generally between 113 and 164 mm (4 1/2 to 6 1 / 2 inches) depending on the weight of the fabric. However, this 3} @st cannot normally be used to distinguish 'different degrees of fire retardant properties! This is the case because a G ewebe- which passes the test. _9-considered fire hens send v / ill, while a fabric _t which fails in this- test, feuerhemmsnde Eigensohaften stripped wordene However, a sample containing only a short Ver-Icohlungalänge bseitEt, not necessary Way more fire-retardant than a second sample ₉ which, although it meets the test conditions, has a longer carbonization length, unless there is a large difference in the carbonization lengths of the two samples. ,

109823/1905

"Q ",

Trots deo Penions clear definitions, relationships or darglciichan has _t verifiable general emerged ^ moin and indeed ignored the feuerliemmsnden agent used that strat for each sub '' and every standard of · feuerhesmmng a minimum phosphorus "galmXt exists nasty? hereinafter referred to as "Gstxn.dphosphorgeha.lt" bs ~. This granophosphorus content is necessary to have a fire-retardant effect. If keys exist which can be used to differentiate the degrees of taxation, a phosphor size is required which gives a given degree of taxation. EvflnüxingBgQm & ae has now shown that the amount of phosphorus can be reduced and yet the fire-retardant properties and / or the Srad Fouerheismung as a treated substrate are retained, the phosphorus is replaced by nitrogen in an amount that is at least three times the difference Basic phosphorus content and the actual phosphorus content is, for example, in the absence of nitrogen at least 2% by weight of phosphorus, based on the oilulose, to achieve the flame-retardant effect on a specific substrate, the same fire-retardant properties are required for a phosphorus content of 0.8 oewiohts- 6 is obtained if the substrate is also treated with at least 3.6% by weight of organic nitrogen.

Even though this relationship between nitrogen and phosphorus is in is broadly applicable, sis is nevertheless more practical

109823/1905

Limited in respect * Usually at least about O _S 2 by weight phosphorus must be placed on the substrate. At lower phosphorus levels, the amount of the nitrogen compound ;, which ssur achieve noticeable fire retardant Eigenschäften is needed _s for a practical application is too high "discarding has nitrogen alone kein® feiiorhommende effect, while organic phosphorus capable of producing such an effect," the other hand wird- " only © in low economic advantage QXisiQXtf if the phosphorus content is substantially lower ala the "O ^ undphosphorgehalt" that Konzopt the present invention Yorstigsw © is lse to actual phosphorus contents bounded ₉ are not grüssar as ungefälir 75 i> and not vorzugsweloe grüossr ALSs ungsfähr 50 <$ " Related to the örundphofiphor content of the substrate.

The Torliögende invention is illustrated by the attached figures . 2 explained in more detail.

■■■ ■ '.. ^: ■ ■ ■■ ■

Figure 1 is a plot of nitrogen content (in ^) versus the phosphorus content (in? δ) that is required to make one char length less than 127 mm (5 inches) on a twill fabric weighing 268 g / m (8 ounces per square yard) to achieve.

FIG. 2 is the plot of the char length against the nitrogen content bal two different phosphorus contents on one

109823/1905

268 g / m (8 ounces per square yard) twill weave

ι,

-In'dar Pigur 1 is the degree of 3? E fire inhibition, as it is defined by the charring length, and is determined according to MTOO 54 * 1952, against the nitrogen content in $> and the phosphorus content in $ _9, each brought into a 268 g / m (8 ounces per square yard) cotton xöper "fabric applied" Haoh this method, a fabric is generally considered to be self-extinguishing, doh "that it is approved of acceptable fire retardant properties if the char layer is at least 127 ^ m (5 inches) is »In 3? On the other hand, a sample with a phosphorus and nitrogen content in the upper right area (area 0) is always self-extinguishing, that is, the carbonization length is less than 127 mm (5 inchos). The border area (area B) represents an area in which uncertainty prevails. In this area an acceptable level of fire retardancy is generally achieved with this particular fabric "ie, a char length of 127 mm (5 inches) or less, but not necessarily in all samples.

The reasons for this uncertainty are not completely clear, however, it is believed to be due to inaccuracies in testing methods

109823/1905

are

The curves shown in aar Pigur 1 can wsrdsn mathematically in the area & ex BiOBphorgehaltevoa 0.2 - 2 ^ by the following equations:

Lower curveϊ

Η »9-% 2.4P ^ 4P ² -2.11 £ 0.2 Ofeero

H ^ 0.25p 4-9 _O 6 »NJ42T4P-4P ² ~ 2.11 ± 0.2

As a result of the above-mentioned inaccuracy, this C'lsic & tmgea. are = ', this ®le.iqhimg (m only door, the substrate used in each of validity ₀ Pur öelliilosegew © "be _s particular swisohen in Bereioli 201 g / m and 335 g - innewohi, ena9 ßenauig & sit not reached"DarU'bei · / ia (6 · - 10 omices per jsrd) the following linaas ¹ © Besishiang is the Phoaphör'bereieh from 0.2.-2 $ as raalietieoiier *

- '■■ "<■' - ■■■ '■' ■ - ■■ '' ■■ N ^ β« 4P ■ ■ ■

A gutor PeuerhenKattjagBgrad {doh * a Yorkohlunelänge of 127 wm. (5 inohöθ) or less) is generally achieved ₉ if the nitrogen content is greater than that of 6 - 43? is »Afohei P fttr the phosphorus content of the tissue is _o

The proportions of the curves explained above apply in general for the present invention, however, they are copied the substrate used. As a general rule

109823/1905

It is assumed that "within a phosphorus range of 0.22 $> a similar fire-retardant effect is obtained, when each P & espharöunheit is replaced by about 4 nitrogen units ₉ related on a weight basis", the constant of the equation fluctuates 3 ^e & ° ch depending on the substrate and the IeSt ₈ the snu? Determination of the euerhemzaandsn effect is appliedc Vev general pressure for alternating nitrogen and phosphorus eats

K - 4P

t / orin K Θΐ & β Eonstanta eats ₈ di. © 3® as the substrate and the standard method fluctuates vxiü. 6 in the vertical flame puff using a 268 g / m ( Botmeee $ ®τ square yard) Baumvoll Eöpi5r ~ C4sv; e "bes} with a charring length of 127 wi (5 inoliee) as the standard for the firebreaking solution Considered νφχΐ. Higher K values occur when the vertical flame release is used with the use of inflammable substrates, or when a more precise definition of the heat treatment effect is used, _for example when a lower acceptable carbon length ^ is used in these treatment methods It is advisable that the nitrogen is present in an amount that is approximately 2.5 times the weight of phosphorus, the combined nitrogen and phosphorus content being at least 3 "5j6, based on the weight of the cellulose _f "

Xn FIG. 2 shows the dependence of the carbon length on the Nitrogen content was shown as two different phosphorus contents.

109823/1 905

Measurements for this graphical representation are obtained in the example. As can be seen _e is made by a rising stick »; oisoffgehalt ÖIE Yerkohlungsläage of the phosphorus-treated Batuswollgewebee rsdusiert noticeably, Be is again out "= 'äwniiiBmi ₉ that although the JJeigimg and nature of the curves in Figure 2 are generally valid for the invention, the exact position of the curve of the specific system, , uad yesar the-'in each case v © £ -. -used substrate and the respective phosphorus compounds used, .depends on the value stshen for & in & 268 g / m (8 ouiaces . g per square yard) ~ cotton g0W © b © sample, which has been treated with a phosphorus compound which contains chlorine. .The property «= · liait voa halogen (Ciilor) increases the tendency to fire resistance as a result of the phosphorus.

As can be seen, the present invention provides a method created after which öis addition of phoaphororganlschexi -Torbinäungen and 'so that the Behaaiwilungskos ben e as well as the night ©! · = · ! ige effect on the physical properties of the treated » th substrate can be reduced while still obtaining a fire-resistant cellulose.

Me is the present invention, although it is quite general any treatment using organic nitrogen and organic, non-ionic phosphorus can be applied, of particular value when the phosphorus content is lower than the phosphorus levels that were previously assumed to be si®

■■■■■ '■ 109823/1905

BApORiGINAL

-H-

allow an acceptable degree of fire heating. For example, the phosphorus content is less than about 1) 3 $> and yoraugswoiee wsnigar ale about 1 #. These reduced phoephormongones can generally be considered to be no more than about 75%, preferably about $ 50, of the base phosphorus content defined above. A feature of the invention is therefore in

* the treatment of cellulose with phosphorus in an amount of no more than about 75%, preferably no more than about 50 $, "possessed of the toundphosphorus, and nitrogen in © iaiar amount, which is less about the 4-fold of the under « The difference was between the basic content and the actual phosphorus gel content amounts to.

The maximum nitrogen content of the treated cellulose is not critical »it was found, however» that an improvement in any phosphorus content below the basic content

* The fire retardant properties are achieved with an increasing nitrogen content up to a point »above which no further improvement is achieved«. This can be seen from the figure. In general, this maximum level will range between about 100 and about 800 pounds of the difference between the base phosphorus level and the actual phosphorus level. An increase in the nitrogen content to a value above these words has no further improvement in the fire resistance.

109823/1 905

.. 'Properties on the following © * Due to the increased addition there is a tendency to deteriorate the physical appearance of the substrate "

The Qril'indraigsgQKäose method thus orders that cellulose K.Lt one or more organic. Compounds treated wii: dg oils nitrogen imd / hiossphor in solo amounts anthaltenj, oils «te-uu -av.preiclienj that s.ia c © llulofsehal ti ges. Product does WiKfI ₈ ilafi Hiospiior tinß Sticks te? ff in the imagining-described "S3,0, \ * ?: Höiig'iii öntMlt"Bio;.} owsi3J, gezi Stielistoff, IMD / or Phosplior "connections Q ^ findungsgomäso niolit 3α · Ιtisch _t i claoB a © ausreichondö Meng © applied to nitrogen and to the cellulose. Bahar can organize connections, - di®. one or more nitrogen atoms © and / or one or more phosphorus atoms containing * can be used. «It is;] ®dooh swecfonässigu .ö.aes. dls vervrendeten organic IFER-Mndungen relat-Ιτ wer4s are volatile, and at least in the awar? orza, in 'weloher present in dom letstlioh obtained celluloae- λ-containing product, and voraugßweiee in the mold, applied in vjelchor they werdsn _s to Ysrluste Avoid evaporation during treatment and subsequent use of the cellulose. In general, compounds are "with a normal boiling point of at least about 200 ⁰ G su · =» peace-sharing »

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BA £ 3 ORIGINAL

- 16 -

Its second beneficial property is its solubility in water, there the application of the agent to cellulose, especially when it is in a textile form, preferably from aqueous media takes place * Since the phosphorus and the nitrogen preferentially in the End product in a form which is not soluble in water, especially in textile products, should the compounds used contain reactive groups To enable intermediate polymerization and / or reaction with cellulose and thereby make it water-insoluble form.

Another beneficial feature is the presence of relatively high levels Amounts of nitrogen and phosphorus in the agents used, so that the desired level of addition of nitrogen and phosphorus is achieved a minimum of added fire retardants can be achieved. Generally a compound or mixture is the Contains at least about 20% by weight of nitrogen and at least about 8% by weight of phosphorus, by weight

As mentioned above, organic compounds that can be used may contain stioketoff but not phosphorus. They can also contain phosphorus but not nitrogen or contain both phosphorus and nitrogen »

Suitable compounds that contain nitrogen but not phosphorus contain, have a carbon-nitrogen bond, where

10 9 8 2 3/1905

Connections in which de? Nitrogen in the form of an afflin «or Amide group is present, are preferred., Of the amld forms are the arboxamid and sulfonamid fora are mentioned, with the oarboxasiid forms being avoided. Particularly "recommended StJLoScatoff- · containing pre-ties are the few "who" have a tie show how you can use the following leilform *! reproduced it will;

> K - O - ΪΓ < (I)

• in which X £ §v Oso,! Ehioxo or substituted or unsubotituted imino stands, ie _rt dees it is about compounds . CIe ₅ I. *., Wtlohe «have απιβυοΓ * -, iL'riioharnatoff- or ouanidine bonds ,, ... ■■"; * '

Me free valenses of the above described bonds may be linked to hydrogen, carbon or nitrogen. Bevors-ugte aoyclieoho compounds which contain this bond, Wimen duzeh reproduced the following general formula | wardent

where X _{1 is} oxo, shioxo or imino, R is a divalent hydrocarbylene radical, in particular an alkylene radical _; with 1 · 5 carbon atoms, R ₁ and IU each mean W · «» er «tofi _t amines,: or hydrooarbyl or bydroxyhydrocarbyl, lne" b "eonder # lucyl or hydroxyalkyl, all with up to about 5 carbon atoms

109 82 37 1 90 S.

m has a value of 0 or 1 and η is a whole number with a Value of at least 1 and preferably 1 or 2 symbolized *

Examples of such compounds are urea, shloharn « substance, guanidine, dicyandiamide, biguanide, semicarbazide, obobohydride, bisurea, 1,1'-xethylene diurea, Ν, Η'-dimethylol- · urea and the like »

W Another class of nitrogen compounds .are the heterocyclic compounds of Tormels

: dn)

in which t has the meaning given above, R- stands for a divalent hydroarbyl group, preferably an alkylene group, with up to 6 carbon atoms, which if it is associated with the group HO (X) H * is a 5- to 6-membered group R and R ₅ are each hydrogen, lower-hydroarbyl or lower-hydroxynydrooerbyl (e.g. lower-alkyl or hydroxy-lower-AXkyl with up to 6 carbon atoms).

iaidasolidin, N, H ¹ -diethyl-2-imidaaolidinone, H, H ¹ -dim * thylol -

Examples are 2-imidazolidinone, 2-imidazolidinthione, 2-iminoiaidasolidine, N, H ¹ -diethyl-2-imidazolidinone, and the like.

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* ■ 19 -

Another class of suitable nitrogen <* containing hetero * eyclic compounds are the ts-Sriasin derivatives of the Pormel:

(IV)

where Rg, independently of each other! for hydrogen, low-hydrocarbyl or hydroxy- or alkoxy-low-hyiirooarbyl (for example rdedrig-AHcyl, hydroxy-low-allyl or low-alkoxyn-leather-alkyl) *

Examples of such compounds are melamine, N ₂ , N ^, trimethylmelaaiin, ^ ♦ ^ "^ g ^^^ C ^ ydrozyaethylJ-melamine, hexakis (metho3 ^ methyl) melamine and the like emibnt"

In addition to these compounds are polyalkyleneimines, and «was preferably those compounds which contain at least 4 nitrogen «· atoms per molecule, with the alkylene group 2 - approximately Has 6 carbon atoms, very valuable nitrogen compounds

Phosphorus compounds that are used according to the invention are organic compounds that contain phosphorus in a non-ionic form.

109823/1905

phosphorus compound derived from a phosphorus hydride or a phosphoric acid can be used. Organoderivatives of phosphine, phosphine oxide, phosphine sulfide, phosphinimide, phosphorane, phosphorous acid, phosphonic acid, phosphoric acid, phosphonic acid and the like can be used. Particularly preferred organophosphorus compounds are those compounds ₉ in which the phosphorus is present in the form of the Phösphlnidin radical ^ ξρ / ^äes EhospMnylidin-RadJLkais / issP {Oj7, the free valences of these radicals being linked to carbon either directly or indirectly via an oxygen atom »

In the case of the phosphinide-in compounds, it is preferable that the phosphorus is linked to the carbon via an oxygen atom is, i.e. that the phosphorus is in the phosphite form, for example in the form of a radical of the Xeil formula:

-J-O

(V)

Phosphinylidine compounds which are suitable according to the invention, can have one or more phosphorus valences that directly linked to carbon or to carbon via oxygen are. Examples of these forms are;

a) The Phosphlnoxydfomi the partial formula:

(VI)

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b) The phoaplat form of the Töll formula:

- O - C

c) The phosphonate form of. Rope formula:

- 0 - 0 — IP (O)

(VIII)

d) The phosphinate form of the rope formula:

* t

Preferred organic phosphorus compounds are those which have phosphorus in at least one of the porms a - o, ie _f the phosphine oxide, phosphate * and phosphonate form, with the phosphonate form being particularly preferred.

The type of hydroerbyl component of the phosphorus compound is according to the invention not critical »This part can consist of aliphatic, cycloallphatiechen or aromatic constituents exist. However, preferred proportions are aliphatic proportions up to jsu about 10 carbon atoms »which are free from diner acetylen! - see unsaturation, such as alkylenes, alkenyl, Alkenylene, cycloalkyl, oyoloalkylene and the like *

109823/1905

Substituted hydrocarbyl moieties can be any suitable have organic substituents. Preferred substituents are those containing oxygen, sulfur, phosphorus, nitrogen and / or halogen · Examples of oxygen-containing Radicals are hydroxyl, carbonyl, carbonyloxy, epoxy and the like. Suitable sulfur radicals are mercapto, thiοcarbonyl, Xhio, Dithio and the like. Nitrogen-containing radicals are for example primary, secondary and tertiary amine radicals, for example the Bydraain radical and the like · In addition radicals that contain two or more of these atoms can such as carbeiacyl, sulfonamido, sulfinyl, sulfonyl, urine Remnants of matter "like the like, to be present", of aea "haxogenaeomen bromine or chlorine are preferred. The presence of halogen has a beneficial effect in that the halogen has one synergistic effect on tax inhibition due to phosphorus * exercises. However, Ss are high amounts of halogen for a synergistic Effect required. The presence of halogen can cause a * cause cellulose to build up, so that halogen is far less suitable as a synergistic component than nitrogen.

The organophosphorus compounds can be one or more Contain phosphorus atoms. Of the monophosphorus bonds, those are preferred which have hydrooarbyl radicals, such as, for example Alkyl and alkenyl and in particular allyl, which are not substituted or with hydroxyl or Bpoxy groups or halogen are substituted.

109823/1905

Be particularly preferred?
a) Phosphites of the formulaί

P (X)

where R «is alkyl or alkenyl of up to about 10 carbon atoms stands.

, Γ

For example, be Slriäthylphosphit, Tripropylphosphit, Xriallyl " phosphite and the like mentioned.

: ■■: '' ι

ti) phosphine oxides of the formula:

(Rq) ₅ P (O) (XI)

wherein H _{8 is} alkyl or hydroxyalkyl with up to 10 carbon atoms and preferably hydroxymethyl.

Examples of phosphine oxides are Xrimethylphosphinoxyd, Xriäthyl <phosphinoxydy l2is (cyroxym6thyl) phosphino3cyd and the like.

o) Phosphates of the formula: I

(R ₉ O) ₃ P (O) (XII)

wherein Rg stands for alkyl, alkenyl or epoxyalkyl with up to 10 carbon st off atoms and preferably allyl or 2,3-epoxypropyl

Examples of phosphates are triethyl phosphate, triallyl phosphate, iEris (2,5-Spo3cypropyl) phosphate ima the like.

109823/1305

■ - 24 -

d) Phosphorates of the formula:

(E ₁₀ O) ₂ P (O) _(mi)

wherein H _{10 is} alkyl with up to about 6 carbon atoms and R _{11 is} alkyl or substituted alkyl, such as Oarbamoylalkyl, N-alkylcarbamoylalkyl, N- (hydroxyalkyl) carbamoylalkyl, aminoalkyl «the Ν, Ν-bis (hydroxyalkyl) aminoalkyl, the to contains about 6 carbon atoms in each alkyl moiety, *

Examples of phosphonates include diethyl ethyl phosphonate, N- (hydroxymethyl) 3- (0.0 ⁹ -diethylphosphono) propionamide, diethyl ff , N-bis (2-hydroxyethyl) amino 7 methylphosphonate and the like.

Polyphosphorus mixtures »which are used according to the invention can leave phosphorus in one or more of the above Forms included. However, particularly preferred are those compounds in which phosphorus is in the form of the Dioxyphos phinylidin-G group is present, i.e. polyphosphonates

Compounds which contain both phosphorus and nitrogen are also suitable in accordance with the invention. A suitable class of compounds are the amidophosphine oxides of the formula;

\ ϊ_ ρ (ο)

(XIV)

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where R.j2 and H ₁ each represent hydrogen or a substituted or unsubstituted lower hydrooarbyl radical having up to about 6 carbon atoms, where R ₁₂ and R ^ * in contracted form are lower hydrocarbylene »preferably lower AUsylen with 2-6 Carbon atoms, for example ethylene, mean each of the substituents H ^. and R ^ - lower ~ hydrooarbyl or a substituted lower hydrooarbyl group, * 'is an integer with a value of 1-3 1st, y and ζ are each integers with a value of 0-2 and the sum of x, y and ζ is 3 . . -.

This class includes:
a) The phosphoramides:
H,

b) 3> ie phosphonamides!

Rh

14th

o) The Phosphordlamidatet

^L 13

HO)

0R- _e

(X7II)

109823/1905

d) The phosphinamides:

(XYIII)

^E 12

^R 13 - (B ₁₄ J ₂

e) The phosphoramide file

R ₁₂ (XIX)

f) The Phosphonamidates

OR ₁₅ (XX)

^ _n P (O)

₁₃ R ₁₄

Particularly preferred are the phosphoramides a) _a. Particularly preferred phosphoramides are those in which the substituents R ₁₂ and R ₁ - each represent hydrogen, alkyl, hydroxyalkyl, alkosyalkyl or aminoalkyl with up to 6 carbon atoms, at least one of these Substituents have a different meaning than oxygen. If R ₁₂ and R ₁ - are drawn together, then these substituents form an alkylene group with 2-6 carbon atoms, in particular ethylene or propylene, with ethylene or propylene, if these substituents are combined with the amido substance, a 3-5-membered heterocyclic ring form. Examples are Sris (1-aziridinyl) phosphenoside, Cris (N-hydroxymethyl-H-methyl) phosphoramide or the like

109823/1905

mentioned, H, li ^l , K ^w -Ia? is (2-AminoäthyX) -phosphoramid is particularly favorable.

Another suitable class of phosphorus and nitrogen containing compounds are the ^ Epo3 ^ aminophosphonates of the formula!

, C £ - ~ $ Η - GH - HH «4 ~ -Q (XXI)

wherein R _{16 s} is hydrocarbyl having up to about β carbon atoms, in particular alkyl, alkenyl or aryl, a is an integer Sahl having a value of 1 or 2 and Q is a hydrocarbon, "or substituted Kohlenwasserstoffreat with up to about 10 carbon atoms having a valence of a represents «

Be-s ο rs ag-'ue connections are those in which a for 1 stands »These connections can be made easily 2,3 ~ £ poxypropionaldehyde, a dihydrooarbyl phosphite and a primary monoamine or diamine manufacture «The process can be carried out in that all three of these starting materials are reacted together or the aldehyde and the Amine first to give an imine of the formula:

^ CHCH «IF-

-Q

(XXII)

be brought to implementation, which then with the Phosphite is implemented.

109823/1905

Another highly preferred class of phosphorus and Nitrogen-containing compounds are the phosphonates of the Formula:

Y-

-R

17th

fa,

Ί7

(XXIIl)

where I in each case represents halogen, substituted or unsubstituted amino or substituted or unsubstituted hydrazines, each of the substituents R _{1 represents} alkylene or haloalkylene having up to about 10 carbon atoms, Z represents a dioxyphosphinylidine radical, b is a positive integer, which is preferably has a value of no more than about 4, and Y _{1 is} T or symbolizes bi- (lower-alfcoxy) phosphinyl, with the exception that at least 1 Υ and Y _{1 are} a nitrogen-containing group.

Particularly preferred phosphonates are those in which each of the substituents I and Y _{1 represent} a nitrogen-containing group as represented by the following formula:

N (NH) ₀ --R,

• 20th

Z-

R ₁

-R

20th

20 "

(XXIV)

wherein the substituents R ₁₈ and R ₁₉ each, if they are taken alone, denote hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl or aminoalkyl, the alkyl moiety being up to approximately

1.09823 / 1905

Contain about 6 carbon atoms, R ₁₈ and R-jg, if these substituents are combined, denote alkylene with 2-6 carbon atoms, where a 5-6-membered heterocyclic ring is formed when combined with nitrogen, K ₂₀ alkylene with 1 Represents -6 carbon atoms, c is O or '1 and b and Z are as defined above.

The present invention is applicable to curable and non-curable finishes. This means that the fire retardant may or may not be resistant to removal during washing.However, in the case of curable finishes, it is of particular advantage if the organic compounds containing phosphorus and / or nitrogen are insoluble in water during polymerization or reaction with the cellulose In these cases the agents used must contain reactive functional groups, for example a group that reacts with the hydroxyl groups that are attached to the cellulose macromolectU The consequence is that a substantial part of the reagent cannot contribute to a fire retardant effect, so a method of decreasing the addition is of particular importance.

The type of treatment of cellulose with nitrogen and / or Phosphorus-containing compounds are not according to the invention particularly critical. The order in which the- » like connections do not matter. In the case of textile fabrics

109823/1905

can the tissue with a solution or suspension of the selected Hlttol will be treated in such a ratio that after the Impregnation a fabric is obtained that contains nitrogen and phosphorus contains in the desired quantities and proportions. Optionally, the fabric can be in sequence with two or more Solutions or suspensions containing the desired individual reagents, are impregnated.

As mentioned above, it is useful if the cellulose with the nitrogen and / or phosphorus-containing compound is impregnated from an aqueous medium. Albeit the use an aqueous medium is favorable, especially in the sextile industry, organic media, such as hydrocarbons, alcohols, amides or the like, can be used. In addition to the liquid medium and the compounds containing phosphorus and nitrogen, can other constituents may also be present, for example catalysts to induce or accelerate the dissolution of the fire retardant composition by polymerization and / or Reaction with cellulose and additives to give the cellulose substrate other desired properties. Shall, for example sextilles containing cellulose are treated according to the invention, then the liquid medium can also be lubricant, water-repellent Contain agents, dyes, crosslinking agents or the like »

109823/1905

. ■; ■ - 31 -

The treatment according to the invention can be applied to cellulose in any Form can be applied, for example to native cellulose, w £ «T2StIQi example cotton, wood and jute, regenerated cellulose, such as cellophane, eeyon and modified Rayon and cellulose derivatives such as cellulose » esters, for example cellulose acetate, hydrosyalkyl cellulose and like that. The physical form of cellulose is not critical. Fibers, films, soluble cellulosic polymers, cellulosic resins and the like are embossed. ' Typically, phosphorus and nitrogen are applied to cellulose-containing resins, cellulose-containing fabrics, especially made of cotton, cellulose-containing yarns which are then used in a fire-proofing Fabrics can be knitted or woven, as well as on viscose or cellulose acetate prior to spinning to obtain a fire-resistant fiber applied. Another application is treating a Heyon yarn or fabric, which then for the production of a carbon yarn or fabric with improved properties and / or improved design prey is used. The invention can also be applied to mixtures made of cellulose can be used with other materials that do not contain cellulose.

Although the present invention is primarily referenced to the textile sector and in particular to woven cotton fabrics has been explained, it is nevertheless in the same way also applicable to other forms of cellulose, for example to

109823/1905

knitted fabrics or nonwovens, paper, wooden saddles, boards, Fibers, threads, seeds and the like. The one described above Char length was used as an index of fire retardant properties used »However, this char length is only for some substrates, such as textile fabrics, and for some Paplerfonaen a suitable criterion for determining the extent of the fire-retardant properties of other forms of cellulose » such as fibers or yarns and the like

^ other SJests necessary. These are optional tests explained in more detail in the following examples “Regardless of the test used, however, the general relationship applies between nitrogen and phosphorus, which was explained in more detail above, to achieve the fire-retardant properties. the Values recorded in Figures 1 and 2 illustrate this relationship and are for specific amounts only with reference to FIG a specific woven cotton fabric applicable only in terms of char length. Similar relationships between the nitrogen and phosphorus content are

"mend properties also in other forms of oil and others Tests to determine fire resistance were observed.

In addition to the synergistic effectiveness discussed above of nitrogen with non-ionic phosphorus, it has been found that organic nitrogen is also synergistic Effect in fire-retardant treatments in which ionic phosphorus «i.e. phosphorus in the form of a phosphor

1.09823 / 1905

- 33 - '"■

phoniumions »is used as a fire retardant. Phosphonium compounds that can be used, nachreohssa the general Pormels

wherein H ₂₁ , R ₂₂ , R ₂₃ and R _{24 are} hydrooarbyl or substituted hydrocarbyl having up to about 10 carbon atoms,. A is an anion with a valence of d and d represents a positive integer number, the value of which is 1 or 2, preferably 1.

Examples of hydrocarbyl substituents on the shosphonium ion are those substituents which are aliphatic (including * - Lich oycloaliphatißdie) as well as aromatic components contain, with for example Α13ς ^ 1, alkenyl, cycloalkyl, cycloalkenyl, aryl, Alkaryl, aralkyl and the like. Preferred hydrocarbyl radicals are the lower aliphatic radicals up to about 10 Contain carbon atoms. The leftovers, which are about € carbon a tome are particularly preferred

33er hydrocarbyl group may be substituted in any desired manner, for example by hydroxy, carbonyl, _e öarbonyloxy- epoxy, mercapto, amino, halogen, sulfonyl Qarbamcylreste country or the like. Preferred substituents for an alkyl radical are hydroxy, epoxy, lower alkoxy and a lower - * acyloxy. Is a & er substituents Rg ₁ - R ₂₄ is alkenyl

109823 / 190S

or aryl, then these beds can preferably not be substituted be*

Bas represented by Λ © Anion can be any suitable anion be, for example hydroxyl, or an anion of an inorganic acid ι where the anion is preferably monovalent. Particularly Preferred anions are the halide ions, such as, for example Bromide and chloride, but other anions also come in Question, for example, hypochlorite, pluoborate and the like.

A particularly preferred class of phosphonium compounds is that Blasset in which at least one of the substituents ^ ₂₁ - H «* stands for a vinyl group or a latent vinyl group, ie a group which yields a vinyl group under basic conditions» Examples for latent vinyl groups are the 2-hydroxyethyl group, 2-alkoxyethyl groups, 2-acyloxyethyl groups and the like. As a result of the presence of the yinyl group, these compounds react, if they are treated with a base, with the cellulose, giving it permanent fire resistance.

A second suitable class of phosphonium ales are those salts in which each of the substituents R ₂₁ - R ₂ A ^{£ üx is} hydroxyalkyl, for example hydroxymethyl. The Xetrakis (Bydroxymethyl) are particularly preferred -> _t phosphonium especially the halides such as the chloride.

109823/1905

The extent achievable using these phosphonium salts in terms of anti-fouling properties can be found in a simple manner by treatment with one of the nitrogenous substances described above ^ -containing organic compounds in connection with the treatment methods using organic, non-organicGm Improve phosphorus. However, those compounds are preferred which have a combination of the rope formula given below:

^ H-O- H < (I) I.

in which X has the meaning given above. In the treatment according to the invention, however, it is stated that the amount of ionic phosphorus is not greater than 1 weight weight, based on the cellulose, and preferably not greater than 0.8 weight weight · = · ^ should be. As stated in the case of non-ionic phosphorus, however, there should be at least 0.2% by weight of ionic phosphorus · The weight ratio of nitrogen to ionic phosphorus should be at least 2.5 · The total g weight of nitrogen and ionic phosphorus should be at least 3.5 weights- ^, based on the weight of the cellulose, make up.

As can be easily seen, the above-mentioned phosphorus and / or nitrogen-containing compounds compound classes, which "are known to impart fire retardant properties. According to the invention it has been found that, if the nitrogen and phosphorus content of the well-known fire

· ■ · 109823/1905

~ 36 -

Ιιβπβα & ΜίΏΐ means in a corresponding relation srixeinandor provides _g one a superior fire resistanto oelluloaehaltigeEj Pro cdi "et can achieve" this "so far were completely ineffective with Faosphorgenaltige ο

The following examples illustrate the invention · Ia dea examples are the following seed methods Qi

1 _e Eleraeatos analysis

a) .The HiosjihorgGhali; If there is a long term separation of the Solioninger method as well as a subsequent oolori ™ Kstrisahen method raxtez pretext of a MolyMMnblau-Komp-sxefi · or according to the Ejeldahl-Method © e as well as an aaischlessenden. colori «n method using τοη Aoeton / Vfesser su ?? Xjv ^ m *

d @ ac Phosplioaolybdate color determined (cf. ", Bernhart et a! o" ilaal.Olieni., £ 2, 440 (1955)) *

k b) 33 nitrogen content is determined according to the Kjeldahl method,

who either

1 _e the colorimetrisohe Hothode according to ifeesler

or 2e a 3) estilXation alo ammonia: with subsequent titration is determined.

o) Dar bovalent gabxmdene chlorine content is through tmter formation of the oil chloride: Lone and an £ iotilies & end silver treauioE.

109823/1905

BATH ORIGINAL

ίί. Vertical planass test - AASCO 34-1952, Yerkolil-

annoying smgsgebßiL ixi um. '

Example 1

Each tone five samples from a Köp © 2? Tissue of lOO ^ igar tree «¥ oll® sdt iron weight ύοώ. 268 g / m (S oimsos paa? Square yard) in an I <uftof8.n 30 mimte ^ i long at 93 «I ⁰ O getrookaoto

Έ & ζιβ V: coloe (A) is obtained by means of qIelqs Iiai) or-Foitlard until au lT>iißii'l »igfe {? I.uSaußaaiffii © toji o9 ^ ro: Lt einer v / Uosru Lööimg impx'il ^ TJlort, the 30 Weight- ^ rockCa ^ -ßpoxjpropylJpiioaphat CfBK ?; and 2,4 Gewehte-ii'SiiÄfluotoora * enldial-t, be: L about 6O ⁰ O gateöoknei; imd aui o.üi »m IMimen ^ Mxiutsn laag at 155- S ⁰ O in ziii-m mlf, Jteuolsluft böheisiOzi 'oven gebäsbet, After washing In öiziei? 0, 'bloody aqueous Jiösung sinsa nioht-ionisolieii Dster «= 7ßm; ie.n ₉ rinsing in Waaßör and öeza ilrookaea the hardened :? Äsa'be üiiiö GsMiohtssuiialvffiQ γόη 8 _S 7 ^ ₈ woboi it turns out, & SS5B 3ie 0.96 .GfsvTiohtB- ^ Biosphor oil holds. The sample burns bsi d © m vertika3.ea J? La.iaaentest in iteer entire

Sine aw & ita Ps ^ obö (B) becomes bia mi a P of approx. 65 «4 55 impregnated with a vaerous Tj3sung _t the 16-, 5 Göwiohts-Ji I ₂ , Ii ^, 3? G« 2: <. ^J XöCHyaroxymsthyl) fficilamin (MSM) ixad 0.3 GGwJ.ohts- 5i ¥ arjserstoffp © ro; Kyd contains, aivf ßinen li '

-of 30- 10 ° / o ^ eteoclmei ;, B Mn '^ tea. long with "

109 823/1905

Serdsmpf treated »washed, peptized and dried» hairy sample is asisGliliosseacl with SSIPP according to the MaInK) Ie impregnated ₉ as used for the Pro'bs A with & © _e Xte.3 © r "ialtsns product, which 0 _s 92 ßeweights - ^ Phosphor τιιιά 3 »β f» nitrogen contains; Mlt, has a length of 102 mm (4 inches) *

Untor iKiwenclnag dar fite the I'robe A s £: agelia.li'sne2i Ji! Ethods is sine - third sample (0) to zn eiiier Fsuchtigksi-feasufashme "/ on 76 / a laJ.-fc einar waasrig ^ n Löoim ^ i-nprägulert, d: ie 30 Gewicfcisa- ·? » SiJPF », 15 Gewiöht0 ~? 5 THM untl 2,4 tlewlohtn- ^ SinlcfluoDora-b öii-b- hä'U'jf vorauf sie aaßciilioanaiid g -r \ z, οο1γλοι5 ₉ geMirtet _s gQwano.b.en _P , 3 © rinse and goteooknet. MeH ^ Probe has a Phospi} .O2? ->_; ^; j ": bBlb * 7o: a 1,2 j", siuoi ". n'b.to'cotofl'gelialt Toa ^, 4 ^ iiad © ine Te?; · * ·

fit; a zws? Treatment of the prob; - · 0 asigewoadet ^ n methods \ iwill treat the probes D _& with the understanding that the impregnation imgö «bad axisaerdem '0.3 Ge'ciohiis ·» ^ water content pero3cyd and the .lmprägniörte sample before dom Bäa ? te; i 8 Minut © 3a la »g ml-fe Wasosrdaxnpf"baliandeli;> jird »Biene sample antlaa.lt 0.96 fo Phcoplior imd 3.4 $ nitrogen and wsiot sine YöEkoh'Vuiigsläage τοη 102 Jisa (4» 0 inches)

Bio le IiK be Proba (B) is duroh impregnate α with '.BW. tind water-αboJ? £ pv.t. «o3cyd naoii which for the treatment ^ ¹ " sample B described-

109823/1905

f- *

BATH ORIGINAL

Bnden.tj; "where- 3o & öoh the Belioiieilumg & aah. the Tor-Sri; * Biea® sample, which 3.5 Clewichtg ~ $ Stioicbreanu in Hirer gQse

Bie SiiioJistcff · ™ and Hio3phcrgelte sawie die Terlcoli3. "Moderately long the Tox-KbQliead "contains the same Pro'oen s: Uid -in the following sabers

Sabelle I

A 0.96 0 BEL

B 0.92 3> β 102 em

C -1.2 3.4 '. 107 ma

J) 0.96. 3.4 102 ma

B 0 ■. ■ 3,5 ■■. '■■ BM.

Me sjiiergistisGhe effect sound nitrogen around! Phosphorus can be seen from this table "Obxiohl either ung @ £ & hr 1 fo Phosphorus 3j5 f> Nitrogen Bur föuerfestmaokenden treatment"

eaia, these amounts, if combined, provide a selected degree of fire resistance. The samples B _t G and D show that the degree of fire resistance is essentially independent of the way in which the components are added *

109823/1905

BATH ORIGINAL

- 40 -

example 2

In compliance with the methods described for the "pretreatment according to Example 1 B", three samples (A ₉ B and C) made of a cottonX twill fabric with a weight of 268 g / m (8 ounces per square yard) are mixed with! Eris ( Hydroxymethyl) melamine to achieve nitrogen content of 4.3 * 4 »3 or 3 * 1 weight ·» ^ impregnated. The samples obtained are then taken up to a moisture absorption of 59 "61 or 65 weight" ^ with aqueous solutions of 20 weight ^ (sample A) or 10 weight ^ (B and C) Sris (1 "aziridinyl) phosphino: syd and 2.4 weight percent zinc fluorate impregnated. All three samples are then dried, hardened, washed, rinsed and dried in the manner described in Example 1A. The nitrogen and phosphorus

Tabel II summarized. II ^ length of communication ^ M * Tabel Gewebesj, ^ S Salary of -JL 88 sample ■ -EJ 6.2 96 A. 1.3 5.9 114 B. 0.67 4.9 0 0.79 example 3

In compliance with Jiethoden, which are similar to those used in Example 1A, two cotton twill fabric samples with a weight of 268 g / m ² (8 ounces per square yard) are used

109823/1905

■. β> 41 ~

Aqueous solutions of a} ris (1-Asiriäinyl) phosphinoxide (APO) and - & uaxiicline (made from aqueous guanidine hydrochloride by increasing the pH to 9.0 using sodium. hydroxide and subsequent mixing with the APO) you impregnated baths contain T2,9 $> APO and 7.1 ° f guanidine (sample A) and 9 »5% APO and 10.5 f> guanidine (sample 3). Di © leuhtigkeitsaufnahme is 70 bsw. 63 f °. The results are in the cable ΪΙΪ

Tabel III rkohlunßslänffe mm Salary of sample JL -JL 109 A. 1.4 3.9 127 B. 1.0 4pO

l 4

In compliance with the working methods as described in Example IA are used, a Bauiawoll "- £ oper ~ fabric with a (Jewicht from 268 g / m (8 ounces per square yard) (sample A) to au

• © izter moisture absorption of 67 ? ° with an aqueous solution of 25% by weight (If-hydroxymethyl-N-methyl) ph © spM © ramid '(114PA) and 1.8 $> magnesium chloride impregnated as a hardening catalyst, dried and hardened , washed, rinsed ismd ge »trocloieto

Bins Eweit sample (B) is similarly M ^ aScIaIt ₉ with "the

109823/190

Exception j that the impregnation bath also contains 15 weight tris (HydxOX2nsiQtliyl) melamine and 0.3 weight ^ hydrogen pe:? and the impregnated sample is impregnated to a moisture absorption of 59 $> and treated with steam for 8 minutes to harden.

A third sample (0) is impregnated to a Peuhtigkeitsaufnähme of 74 ° with an aqueous solution containing 24 »3 weight-56 ΪΜΡΑ, 19.4 weight ^ Hemkis (methoxymetnyl) melamine (sold under the trademark" Öymel 301 " from the American öyanamid Go,), 0.9 weight "^ magnesium chloride and 2.9 fo a 30 $ solution Onea amine hydrochloride, is sold under the trademark dsm" XEP "from Onyx Chemical Oo _β" contains. To Sample closing is dried, _"s gebartet washed, rinsed and dried.

The results of these experiments are summarized in! Table IY «
■ Table IY

salary of the tissue ^ f '' Carbonization plans, mm sample JL JL A. 1.2 1.0 BEL B. 0.85 3.4 119 σ 1.1 3.0 127

109823/1905

In compliance with methods ,, the the gomäse Example 1 A to-.gewendeten ähnlieh ₉ is © in cotton E: ~ Öper fabric having a weight of 268 g / m (8 ounces per square yard) (Sample A) zn cdnsr Feiichtigkeitsaufnahme of. $ 77 with a watery one

..impregnated, the 38 weight · * ^ H- (Hydro25: ymethyl) ~ 3- (O _i 0 ¹ ~ Mät} Lylphosphono) propionamide (HMPPA) and 3 »O weight ^

"XHP" solution contains "Kie sample is ansohiieasend getrock" for 5 minutes cured at 17O ⁰ C and rinsed.

A second sample is loaded in the manner described above. hsndeltp- whereupon © / © ending in a further impregnation to au feuchtigkeitsaufnalime of 75 i> imter Yer \ an aqueous solution is carried out, which contains 15 S ^ 2ris (E3rdrosymethyl} melamine and 0.5 $ Waeeerßtoffperoxyd. Ansehliessend ^ IIRD the sample getrocimetj , treated with water vapor and cured in the manner described in Example 1B.

Sins third sample (Q) is treated to a au feuchtigkeitsaufnähme of 65 $ »■ with an aqueous solution containing 25 weight ^ lind 20%" Cymel 301 includes ". Subsequently, the sample *

dried at about 60 ^{° C.} The results of these tests are summarized in Table V below »

109823/1906

salary table 1 Charring length ^ mm P. of tissue, ^ sample 0.75
0.62
1.2 H 96
127 A.
B.
C. 0.59
5.3
2.7

A comparison of Samples A and B indicates that a sufficient amount of material is required. For example, sample A has no fire-retardant properties, while sample 3 has excellent fire-retardant properties, namely despite the higher phosphorus content of sample A ₀

A sample of a cotton twill fabric with a weight of 268 g / m (8 ounces per square yard) is up to a fire resistance of 71 % with an aqueous solution of diethyl / f ,, H'-bis- ^ -Hydro ^ äthylJaM ^ Tmethylphosphonat (sold under the trademark "Pyrol 6" by Stauffer Chemical Co.) and then dried.

Three further samples (B, C and D) are first treated with an aqueous solution of 16.5 "11.5" and 7.25% by weight (hydroxymethyl) "melamine and 1 , 0 f ° hydrogen peroside impregnated, dried to a moisture content of 30 ° 10 96, treated with steam for 8 minutes and immersed in a 0% aqueous solution of a non-ionic

109823 / 190S

see Detergensas purged The three samples are then bia impregnated to a pickup of about 56 # and anschli © esend with 8,6-, bsw 17 »O- * 27 ^ _P O- aqueous solutions-won" Fyrol β "rinsed and dried . JThe results of these experiments are summarized in the following table?

Gehali Sabelle 11 Charring ^ slän ^ e ^ imn P. _{ba @ e} tissue ^ sample 2.4 : JL BEL A. 0.49 .; ■ 1.1. 122 B. 0.97 4.7 124 0 .1.5 3.6 109 S. 2.5

Pulp samples (A, B and 0) from a BaTimwoll-Köper-iyewebe with a ©riam weight -wan 268 g / m (8 ounces per sguare jard) are up to a light absorption of 85, 75 bsw. 73 sS.mit 'is H, L? -Dim © thylforiaainid-Iiöaungen impregnated di _t © 50, 32 or 25 contain * f "a chlorinated polyphosphonate, daa under the Waransei CHSN" Phosgard G-22R ^fi from the Monsanto Chemical Go sold ₀ is and'of the formula

OH ₃ GE ₃

Gl GH ₉ GH ₉ OP (O) -OGH - P (O) -OGH - P (O) (OGH ₉ GH ₉ Gl) ₀

^ m € mm Ctm Cm

.tfäprioht. The samples are tme chll ο being end

109823/1905

- 46 -

Six further samples (D «J) are first impregnated with aqueous S ds (hydroxymethyl) melamine (TiM) and hydrogen peroxide., Partially, dried, treated with steam and rinsed in the manner described in Example 6. They are then treated with "Phosgard" in the manner described above! The Badsiisanmensetaungen are "as follows *

Second

• above 9.0 H ₂ O ₂ , $ Moisture ■
recording ₉ fo • XbotguOI \ $> Feuehtlg & edts » D. 12.0 1.0 77 10 69 E. 16.0 1.0 77 6th 65 20.0 1.0 78 6th 62 G 24.0 1.0 82 6th 60 H 28 ₉ 0 1.0 79 β 59 J 1.0 78 6th 57

A last Proba (K) is impregnated up to a total of 82 fo by means of an aqueous solution of 36 ₉ 0 f * WtI and 1 ₉ 0 ί _fc hydrogen peroxide, partially dried, “treated with water vapor” and rinsed.

The results of these tests are summarized in the l'abcille Ul:

109823/1905

salary cases VII Kohlunjeslän ^ e, mm P. of the tissue »j £ * sample 4.4 , -JL 147 A. 2.9 0 157 B. 2.3 0 AT, C. 0.97 0 127 B. 0.56 2.5 · 170 E. 0.54 3.2. 122 Ϊ 0.52 4.7 104 Q 0.51 5.8 99 H 0.50 6.7 91 J 0 3, β BEL K 8.6 :, based on the composition of the bath and the "Calculated would take up.

The above statements clearly show the synergistic effect of nitrogen. In the absence of nitrogen, "up to a phosphorus content of 2.9 $ no fire-retardant effect is observed, and despite the high chlorine content of" Phosgard ¹¹ . In the absence of phosphorus, with a nitrogen content of 8.6 i * , no fire retardant effect is found either. On the other hand, excellent fire-retardant properties are determined with only 0.5 - 1 f ° phosphorus, if nitrogen is in an amount of 8.6 - 2.5 ^ sugegen.

109823/1905

ilMSÄt Wi

OH 8ft

(Ö) p - öö: ö

(ö) i?

Ulfe Prötie id.M

2 & M

4 »

Two wö ± ies? Ö ΐ

become equal, and M ^ as? iii elnöJi RäiJSieii öin | @ s $ iilüiti a 20 ^ igen ibsting föa Ö & rns-fcöff (irobe B) or ^ (Pröfee ö) sprinkled; tib bei a siiireguiiorbare, fedt-operated fuel apifitöiö is vferwettdet «, this for örfinäungsgeMsseli irilöiiMig dös S-iiib £ & tö £ fgiMiii; IUM ^ e this V ^ röisBiiö iind in the föigenSeli T

γ · es ο "^; :

- Salary Tabel VIII t * ■■ ^ e rkohlu ^ slän ^ e.mm 150 t of the Ge - 109 sample Q, 9 ι - - asu WBMm 1-24 A ■: ". - ν 0.9 1 »2 B. ■; ..-- ' 1.0 4th "O G: ■■■ 3

* Calculated based on the concentration of the solution used and weight gain.

Two samples of a cotton twill fabric with a weight of 268 g / m (8 ounces per square yard) are made up to a moisture absorption τοη 100 ^ with an aqueous solution of 15 * 2 weight ~ $ N-CHydroi ^ piethylchloroacetamide and 3 Sewichts- ^ "XSF" -Lcieung impregnated, aizf a frame, ^{dried at 60 0} C and cured for 15 minutes in an oven operated with hot compressed air at 150 ^{0 O.} The treated samples, which

containing <\ point after rinsing in a 0.1 $ aqueous Iiösung a non * "ionic detergent, and after the subsequent rinsing with water and drying in an oven during a hand Panna of 30 minutes at 93- 1 ⁰ O a content of 2.3 '$ ■ chlorine, 1 _s 0 ? * nitrogen and 2.0 fo formilflohydrate, as one analysis shows «

Each sample is * atxsofclleesend in 600 g of a 25 ^ i gen -Lötinng mm

109823/1905

«, 50 -

Iriäthylphosphit immersed in N, N ~ dimethylformainide. After heating under reflux for a period of 3 hours, the samples are removed, rinsed with dimethylformamide and with water and then dried. The sample contains 0 ₉ 1 Kllliäciuivalente / g chloride, 1.1 and 1.35 # #Stickstoff phosphorus, such results in an analysis. .

Each sample is ansehliessend one hour at 95 ⁰ O in which their weight 30 times of an aqueous solution of 2 f * Sodium «carbonate and 0.5% of an anionic Peter Genses (N-substituted Natriu3a" 2-CMethylamino) äthanaulfonat) immersed " laughing a renewed £ roc3caung and repeat the conditioning 3 © de sample contains 1.1 $> nitrogen and phosphorus 1.34 f ° "

Sine sample "and that the sample B ₉ is in the 'be in Example 8 ~ © n inscribed manner aur producing a EWEB © © contains 3 ₉ 1.26 36 4.5 phosphorus and nitrogen $ ₉ sprayed with urea"

Sample A shows a char length of 160 mm (6.3 inohss) * while the carbonization length of sample B su is only 88 aim (3.5 iachos) is determined. This again shows the need for sufficient Nitrogen content in order to achieve good fire-retarding properties KU.

In compliance with Meiiiodon, which the. in

109823/1905

■. -. -IH-

ähnlieh äiinM ^ is a Bäuawöli twill iäit a weight of 268 g / m ² (8 ounces per yard sqimre) ". siäig impregnated up to a Eeuehtlgke .. · ta of 56 $ £ with an aqueous l, the

i (ÜJHPÖ) enMolds. including

di® ftohe "at 65 ^Ö Ö

Three further samples (B, Ö tmä 33) xferSen up to a capacity of about 70 ft Mi aqueous solutions, which are 7.25, 11.5 "and 16 * 5 f ° 2riö (^ äroätymet1iyl (SMi) and Oj 3% ¥ äs3 © Kö "feöffperosyd unfold * Prepare samples t®ilMiiäe getiocläieti Büi steam treated, washed * gseptiXt tuad after dör in example 1B described Metliöd © getroGloiete Each robe is adjoined in the preceding manner E & t SHPO treated.

A fifth sample (E?) "Wltd silts 5MM in the amounts _f as it is for.

al © Prob © -S © ingijsetät ^ r @ ^ d © n _e pre-oiled, then. nöchatö, ls to

su a 3? euehtig3Eeitsaufnahir.e ^: - from 35 $ with 4 ₉ 1 $ igein aqueous r \

ΉΪΒΌ impregnated and

A sixth sample (P) becomes up to one from $ 75 impregnated with an aqueous IrSoul, the $ 16.8 SMM and holds 19.4 $ 2HP0 Qiith. The sample is then dried,

lins last sample (G) is treated by a method which is similar to the method used for sample I,

■ iö9i23 / 1-9-Ö8

«· 52 -

Exception that the ΈΜ düfceh £ 1.6 j6 MaidäBölidinon © will be

The results obtained are shown in the following table X

JL .X, 1.0 0 0.97 2.1 0.99 3.3 0.92 4.4 0.47 4.5 0.9β 4.0 0.90 4.0

P Prgbe
A.
B.

C 0.99 3.3 109

B 0.92 4.4 96

117

G 0.90 4.0 73

I3inö sample with a size of 24,000 ϊα (26 * 680 yards) consisting of one strand. BaTimwollgaioo. (23? 70 ra per (11,760 yards per poimd)), which is wrapped in a perforated cylinder, is in a SpuJ.enf & ebsmciohino 15 minutes long tsei 82 ⁰ C mj.t the 8.7-feohen her »Gov / ifüitöfi one watery

from 2 § per 1 "Surfcix WO" (a sulfatier * es Propryloleut, the τοπ the E ₆ P ₀ Hougliton & Oo »in the trade gobraoixt Mrd) τχνΛ 0.5 S per 1" 5rito: i X-IOO "(a out

109823/1905

BATHROOM OFIiQINAL

existing non-ionic interfacial active agent, that of Rohta & Haas. Go »is brought onto the market) moistened and rinsed, whereupon the liquid is drawn off and drying at 65 ⁰ G takes place. The sample is then at 15 ⁰ O 5 minutes-long automatic cyclan with 8.7 times its weight in an aqueous solution, the 123.5 g per 1 2ris {Hydro: H ^ ethyl) melamine and 10 g per 1 hydrogen peroxide contains, exposed. After the liquid has been drawn off and the yarn package spun, the moisture absorption is 90 fo. The packages will be treated for 90 minutes at 110 ⁰ G with water vapor. After centrifuging for 5 minutes, spilling in cold water for a period of 10 minutes, rotating again for a period of 5 minutes, drying the air and cleaning (seDuring), it is found that the Sam 4 »β $> Contains nitrogen. This yarn is then 'mechaiiisoh' knitted into a fabric »

liach methods which are similar to that described in Example rg i A is the, Clao tissue ämprägalert up to einsr Eeuchtigkeitsaufnähme τοη 108 ° f> horse öiner aqueous Lfjnimg ,. which contains 20 weights- ^ Sri0 (2 «> - Epo) 39prop7l) plio ^: öpliä-ä unä 2.4 Öewichts- ^ ^ ijikfluoborat. In a ciiee © way a Phofjphorgo content of 1.2 i> proves. This product exhibits a coal oil oil of 102 ram (4.0 inches); ■■■;

109823/190 5

Example, 12

Bas Example 11 is ^ except "ea ^ et | a:>ue" be by a 7.1 cent $ Lösimg of "Pnosgarä C-22S" in I, ll-I) iraethyl £ omaiBid Mb zra a Feuohtigkeitsaufnahm © of 104 fo is impregnated. The phosphorus content of the fabric "is $ 1.0. The treated GiawelJö shows a cabbage mega length of approximately 127 mm (5 inchesea).

" ^r Example 13

Example 11 is repeated, with the exception that the epoxy phosphate is slightly different from that in Example 8 of poly (minopolypliooplioitat and S ?? in {A25i3? Iainyl) p2iosphixit ₅ x.jd Yerx'endet. Each of four samples is treated in an "aqueous impregnation bath _{" which holds 5.0, 7jo f} 10.0 "or 13 * 0 Cre- ^ sinss of each agent 105, 112, 112 T ^ sw. 116 ^. Me irrodiikts "baaitsen © ί.Ώ / 3Β nitrogen content of 5» ö ~ 3 $ eov / ie Phosp ^ orgalialte of O ₁ 71?

tr O ₉ 96, 1.1 T) BV. .1,3 #. Mo exitepxecheriden Yez- .fcoIalyngelMn ^ sra Ijε-

■ fcragan 109, 99, 86 or 81 mm. (4.3, 3.9 »3.4 ¹ UnU 3 ₃ 2

Example 14

2woi Gn; .ppen from 5 samples each (AE "and? -] £} so'dLe a group slub 6 samples (! (WQ) from Iifcyon-Oh.aly werdfui am to onei ^% ."? Eaob. · Tigkeltsaufxialime of 112- A- fo impregnated with aqueous LSsiingan, dlG migofäl "! ¹ '.55 5", $ 27 or 20 ^ dee in Boispi-jl ö fceaciir: Lebi- ■ mm. Po'iyairiii-.oj) oJ .7p.Uoöphon? ^; O contain / i «Otb ': ieä -.-: Civappe ün-uh-l"!.!;

10 9823/1905 BADORlGfNAL

the Bad Harneitoff in the following Xonzentral ionan? O $>, 2% 5.9 % 5.7 $ and 7 »6 $> (as well as 9.4 i> for the Pro ** Q) ·

The results of these! Tests are shown in the following table. sanaaengef as s t:

! Table XIV

salary des GowebeSj ^ * yerkohluu. ^ ßläiigeai ixOjae J? _ JL A. 2.1 2.5 99 B. 2.0 3.2 107 O 1.9 3.7 114 D. 1.9 4.3. 89 25th 1.8 5.3 102 I. 1.6 2.0 145 G ■■ 1.6. 2.7 165 H 1.6. ■ 5.6 114 J ■ ' 1.5 4.3 109 K 1.5 5.1 94 Ii 1.2 1.4 BEB M. ■ 1.5. 2.4 BEG H 3.2 BEL O 1'.?. " 3.9 193 P. r »2 4.7 11? Q 1.1 5.5 127

109 823/190 5

172017

The importance of increasing the nitrogen content oil Phosphorus content comes from the in the E & foeile ΧΪ1Γ 2uöaßßä§3ig @ f &; sten Values. With a l & öBpiiöa? Gehait iron tmgefä & r 1 $ eats η © noticeable change "when varying the

from 2.5 - 5s3 feet fosstauiteiiess «Bel

ΐ / ir-a however du ^ eli increase in the strength of the substance «

clearly the need for fire

BUädel from 14Ö ßärüeft ädt el ».er it & tigö Töft ag uift (1 yon one strand of a cleaned building roll yarn made from egg strands (23,770 m / kg ( aüegeöcliiütten ttüt irdt üäöörigeii

Contain »EÜö fföfeöil WöMen aüschlisösößM Getr§ © Met (aj ä Mihtitea laag Mt Waösefdaiäpi tehaiidöit © dor (Ij) 5 laug tiei töj« 2 ^Ö Ö attachedi What they ate, kööiesaoiiS and dried B§hajßiitmgöiEtsÄ © ie ^ t in the following table

Prefoe & JPQ TKM mW *) * ELO

A. to, 5 2t, 8 B. 10.4 2M O 20.8

0 O ₁ ^ O 70 fs)

Ö * i§ 72

Φ 11

1ÖIS25

Bath compositions Moisture θ- Nao .bahaiil giht ^ absorption «$ lung ,

? above
■ ΜΗΗ ι APO EMM Zn (BP ₄ ) ,, H ₂ O ₂ 75 (D) D. 10.4 20.8 2.26 0 75 Ca) B. 20.5 7.5 2.24 0.28 74 Ca) 20.8 7.5 2.26 0 73 Ct>) G- 20.8 7.5 2.26 0 78 (D) H 22.6 11.3 2.26 0 77 ■ Ca) J 14.9 14.9 2.24 0.28 75 Ca) K 15.1 15.1 2.26 0 74 ■ (D) Is 15.1 4β 1 2.26 0 75 Ca) M. 22.4 ■ 11, i 2.24 0.28 78 Ca) N 22.6 11.3 2.26 0

Each bundle is tested for its fire-retardant properties by exposing the bundle _9, which is held in a horizontal direction by means of tweezers, to a 25 mm high gas flame from a micro-burner for 2 seconds. The time in seconds until the flame and the gliminan go out is measured. This time is 36 seconds for an untreated comparison sample. The values for the treated samples are summarized below: -

10 982 3/190 5

salary Table XV Time, seconds 10 JL des ßamß. # * - 5 robe 0.5 JL 7th A. 0.5 5.0 6th B. 0.5 5.7 8th C. 0.5 6.1 7th J> 0.8 6.7 5 B. 0.8 2.3 2 P. 0.8 2.3 5 a 0.8 3.8 4th H 0.8 5.6 7th J 0.8 4.7 3 K 0.8 5.0 4th L. 1.2 5.8 M. 1.2 4.7 N 4.7

■ ^ Calculated based on the bath composition and the increase ο

example 16

Bundle of 140 yarns with a length of 25 mm (1 inch), dii? it has been cut from a strand of rayon yarn (20 100 m / kg (10,080 y & rdß / pound)) made from a paser. " bis su oiner Fouo.htigkeitaaufnaltrrs V '.' r. ^r 'O - Oi) ^c /> me, · - , ·? .- ■■

109823/1905

? the represent ± Ά "Example 14 Ms & hrielaeiieii I» ol3raminöpolypliöBp Hoen, t / Har3iEi: off-2uBaiiMeiiBiBt2tmgöii impregnated MschlisöBend v; ero.en these samples after la Example 15 hescfcriebenöxi method on their PeuerTieetändiglEeit tm-fcersucht "33ie Brgebnißße dieeer.. Experiments are summarized in the following table:

iaböile

Salary of the G & rna * $> * time * seconds

7 4 2 2 2

A. 1.4 1.6 B. 1 * 5 2.4 C. 1.3 2.6 D. 1.4 3.5 E. 1 # 4 4.0 ■ p 1.1 1 * 5 G 1.2 2.1 H 1.2 2.7 J 1.5 3.2 E. 1.1 3.7 Il 1.0 1.1 M. 0.8 1.6 IT 0.9 2.4 O 0.9 2.9 P. 0 _t 9 5.5 Q 0.8 4.0

8 5 4 4

10 11

7 11

P. 13

10 9 8 2 3/1905

Example 17

The series of tests of Example 14 is repeated with the Exception that filter paper is used as the substrate, dae bis is impregnated to a depth of 119-5 $. The results of these! Estes are summarized below »The Fire resistance is determined by means of the vertical flame test »

Table XTIX

Salary of Paper _f $> * Terkohlun ^ slänpe «mm sample JL. , J ₁₁₁₁ A. 2.1 2.6 112 B. 2.1 3.3 127 σ 2.0 4.1 94 D. 2.0 4.7 94 E. 1.9 5.4 104 1 1.7 2.0 127 G 1.7 2.9 117 H 1.6 3.6 102 J 1.6 4.4 119 K 1.6 5.3 94 Ji 1.3 1.5 229 M. 1.1 2.2 208 IT 1.2 3.2 180 0 1.3 4.3 114 P. 1.2 4.8 137 Q 1.1 5.5 117 "Calculated

109823/1905

An untreated sample burns in its entirety.

Example 18

Seven samples of spruce wood chips are dried for 30 minutes in an oven at 93- 1 ⁰ O. A sample is soaked for 30 minutes in an aqueous solution containing 20% by weight 5S 2ris (2,3-epoxypropyl) phosphionate (SEPP). Three samples (B - D) are immersed in similar DEPP solutions, except for the 11 »7» 15 »? and 19.6 contained & urea. A second group of 3 samples (E - G-) is immersed in similar! DEPP solutions that contain 14.0, 18.8 or 23.4 # fris (hydro27methyl) melamine (! EMM) instead of urea. Samples H and J are dipped in a similar catfish in aqueous solutions containing 15 ^ urea and 20 $> IMM. A © last sample (K) is soaked in water.

A 0.5 g portion of each treated sample for 30 minutes ^ dried down at 93 ^ 1 ⁰ O and to a wire grid, which rests on a hing. A 25 mm (1 inch) long gas flame from a micro-burner is applied to the sample from above at an angle of 45 ° for 5 seconds. The time in seconds until the flame and the glow go out is noted for each sample. The results are summarized in the following table:

109823/1905

Table XVIII Time, seconds salary of the wood, # * JL JL > 1O 1.6 0 <i 1.9 5.6 1.7 6.6 1.7 8.6 3 1.9 5.9 1 1.7 7.4 6th 1.8 9.6 · ■

B 0 D

H 0 6.7

J 0 8.0> 10

K OO

^ Calculated based on the bath composition and the weight « St increase ·

example

Using methods similar to those described in Example 1, a sample of a cotton twill (268 g / m (8 ounces per square yard)) is dried and up to a Feuohtigkoitsaufnahme of 32 ⁰ P with an aqueous soluble, from 7.9% by weight of Iotrakis (hydroxymethyl) phophanium chloride _f

109823/1905

16.0 weight-? 6! Πris (Hydroαςymβt3lyl) melami3l and 9.9 weight · $> urea impregnated »The sample -will then be attached at 85 ° < ^? dried for 4 minutes cured at 14O ⁰ C and purged of a non-ionic Datsrgenses with a 0 »# 1 aqueous Iiösung. This sample, which contains 0 _B 68% phosphorus and 5 * 8 ^ nitrogen based on the bath composition and weight gain of the treated sample, shows a cooling length of 107 mm (4.2 inches).

Bas Example 11 is repeated _t except that the impregnation bath contains 8 weight 2 ^ © tetrakis (Hydroxyiaethyl) phosphoni "amchlorid, 725 ßewiohts- ^ 2ris (1-Aziridin3rl) phosphinosyd and 1.95 weight" ^ Iriäthanolamin. The sample is impregnated to a moisture absorption of $ 105. The product contains $ 1.65 phosphorus and $ 6 nitrogen and exhibits a carbonization length of 88 mm (3.5 inches).

Example 21

Animal samples from Eeyonchaly 30 minutes in an oven at 9ji 1 ⁰ O dried and ansohliessend up to a pickup of 134 ^ 4 S ^ with an aqueous solution of IetraMs (HydroxviQethyl) phosphonium chloride (2HP0) _f iris (hydroxymethyl) melamine (SMH )., Urea or iriethanolamine (IBA) impregnated.

1098 23/1905

Bath composition, <$>

sample TSBQ '2BB urea gEA A. 15.3 9.2 9.6 2.9 B. 10.3 6.2 6.4 1 * 9 0 7.7 15.5 9.6 2 _S 9 5.0 10.0 6.2 1.9 After a 9 st in one Furnace at a se mperat

93- 1 ⁰ O the following results are determined:

sample JL Ii
mmmsmn A. 1.8 6.9 B. 1.2 5.0 σ 1.3 9.5 D. 0.9 6.7 * Calculated

Table ΧΧΪ

content of & ewebea _t $ * "charred angral length.mm

ATi

99

Example 22

Using methods similar to those described in Example 1, five samples are made from a cotton twill
(268 g / m (8 ounces per square yard)) with TriaCHydrosymethyl) - = melamine and hydrogen peroxide to achieve an initial nitrogen content of $ 1.7 (1 sample), $ 2.6 ^ (1 sample) and $ 8.5 ( 3 samples). These five samples as well as two not treated

109823/1905

~ 65 -

Delte samples are treated with an aqueous solution of bis (9-Hydrox5-1.4 »7-5Grioxanonyl-% hydroxyiaetÄyl) pliosphonate impregnated. The phosphorus and nitrogen contents (calculated) as well as the carbonization lengths of the samples are summarized in the table below!

Sabelle XXII

0.49 0.1 1.2 2.3 1.1 7.5 2.2 0 2.2 1.3 2.2 6.3 2.9 0 Example 23

e _t mm

BBS BEE. 122 BEjD BEL

BM «

Each of three groups of six samples from a cotton twill (268 g / m (8 ounces per square yard)} is treated with Sris (hydroxymethyl) melamine and hydrogen peroxide according to the method described in Example 1, samples being obtained which have 0 ? £ " $ 4.9> v 6.1 ft, 6.9 #» 8.6 fi or 9.3 $> contain nitrogen per group. Each group is then impregnated with a solution of $ 9.45 ! or 60% Eetrabutylphosphoniumbromid in dimethylformamide containing, namely, the impregnation is carried out up to a leuchtigfceitsaufnähme ungsfähr of 45 ms * 60 ungefälu i> Anschliefstsend a .Irookrcuag carried 1jo:.. L -55 ⁰ O, "the ZhuByl.

109823/1905

and nitrogen content of the samples (calculated) based on the Bath composition and moisture absorption) as well as the observed char lengths of the treated samples are In summarized in the following table:

Table ZXIII

$> P.

0.39 * 0.04 O HEI *

w 4.7 ll

5 | 8 BED

6.7 BBL

8.2 112

9.0 122

1.8 i 0.1 0 BEL

3.9 122

4.9 114

5.6 119 % 7.0 83

7.7 91 2.3-0.1 0 BEL

3.6 104

4.4 102 5.2 9.)

6.5 ü1 7.0 -V5

1098 1 Ϊ .'130 5

Claims (1)

Claims A process gum Ssuorfestmaohen a celliilosehaltigen substrate dureh treatment of the substrate of an organically Rait © ^ non-ioiiisohen & Bhesp it? Containing compound ,, characterized in that the _s Subs sit treat the compound in such Mengti "that the Biosphorgefcal'ö of the substrate is less than the basic phosphorus content, which is necessary si to the substrate fire retardant properties © ?, give "and with m an organic nitrogen-containing compound in an amount sufficient ssur Peuerfestmachung treated ιιίχύ, ο 2ο Method according to claim I _9, characterized in that the treatment is carried out in such a way that the phosphorus is present in an amount which is at least 0 _g 2% by weight, based on the cellulose j and not more than about 75 grains-505, related to the basic phosphorus content, and the nitrogen is present in an amount which is at least 3 times the difference between the basic phosphorus content and the actual phosphorus content » 3 · The method of claim 1, characterized in that DAEs the treatment is carried out such that the phosphorus content is ₈ * not larger than about $ 50 dee ßrundphosphorgehaltes 109823/1 905 4. The method according to claim 1, characterized in that a treatment agent is used in which the phosphorus in I ¹ OIm at least one phosphinidine residue or a phosphinylideinrest and the nitrogen in the form of at least one amine residue, an orboxamide residue, a sulfonamide residue, a .Phosphoramidorestes , a urea residue, a ihiourea residue or a guanidine residue is present. 5. The method according to any one of the preceding claims, characterized characterized in that a treatment agent is used in which the phosphorus is in the form of at least one phosphite residue, a phosphine oxide residue, a phosphate residue, a Phosphonate residue or a phosphinate residue and the nitrogen in the form of at least one amine residue, a carbonamide residue, a Urnetoffrestea, a Guanidinrestes or a phosphoramide residue is present. ^ 6. The method according to any one of the preceding claims, characterized characterized in that a treatment agent is used in which the phosphorus is in the form of a phosphonate residue. 7. Fire-resistant cellulosic composition, labeled by a cellulose-containing substrate, which is combined with an organic, non-ionic phosphorus-containing compound 109823/19 05 dung to produce a phosphorus content of approximately 0/2 ^ By weight, based on the cellulose, up to about 7? #> based on the basic phosphorus content of the substrate, and with an organic nitrogen-containing compound in a for imparting fire-retardant properties to the sub strat sufficient amount has been treated. 8. Composition according to claim 7 »characterized in that the phosphorus content no greater than about 50 #, based on on the basic phosphorus content, and the nitrogen content of the Substrate at least 3 times the difference between the basic phosphorus content and the actual phosphorus content amounts to, 9. Composition according to claim 7 »characterized in that the phosphorus in the form of at least one phosphinidine residue or a Phosphinylidinrostes and the nitrogen in the form of at least one amine residue, a Carboxamidreetes, a Sulphonamidrestes, of a phosphoramide residue, of a urate - = - residues, a Shioh & xnstoffrestes or a guanidine residue is present. 10. Composition according to claim 7, characterized in that the phosphorus in the form of at least one phosphite residue, one Phosphnlnoxydxeatee, a phosphate residue, a phosphonate residue or a phosphinate residue and the nitrogen at least in foam of an amine residue, an Oarboxamidrestes, one 109823/1905 Hams-fcoffrost es, a guanidine residue or a phospl amide residue is present 11 «Composition according to claim J _9, characterized» that the phosphorus is in the form of a phosphonate residue. 12. Composition according to claim 7, characterized in that daoa by treatment with an organic ;, non-ioni-Β see phosphorus containing compound achieved phosphorus content about 0.2 to about 1.3% by weight, based on the cellulose, and an organic nitrogen containing compound has been used in an amount sufficient to render the substrate fire resistant ο 13 «Composition according to claim 7», characterized in that the weight percentage of nitrogen based on the cellulose, corresponds to at least ^ Leie amount, which is defined by the imprint Z ~ 4B , where P stands for the phosphorus content ^ and K is a constant with a Is the value that depends on the substrate and the test used to determine the fire resistance 14. Composition according to claim 13, characterized in that the substrate consists of a cotton fabric and K stands for the value 6 109823/1905 15 * Composition according to Claim 7 »characterized in that the phosphorus in the pona of a phoephonium ion is present in a range to provide about 0.2 to about 1% by weight of phosphorus, based on the cellulose, and a organieche, nitrogen "-containing compound is present in an amount sufficient to ₉ to render the substrate fire resistant * 16. Composition according to claim 15 »characterized in that the phosphorus content is not more than approximately 0.8 fo . 109823/1905 Lee r side