CA2054759A1 - Flame-retardant composition and use - Google Patents
Flame-retardant composition and useInfo
- Publication number
- CA2054759A1 CA2054759A1 CA 2054759 CA2054759A CA2054759A1 CA 2054759 A1 CA2054759 A1 CA 2054759A1 CA 2054759 CA2054759 CA 2054759 CA 2054759 A CA2054759 A CA 2054759A CA 2054759 A1 CA2054759 A1 CA 2054759A1
- Authority
- CA
- Canada
- Prior art keywords
- flame
- weight
- preparation
- ammonium
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
- D06M11/71—Salts of phosphoric acids
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Fireproofing Substances (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a flame-retardant preparation which contains at least an organic nitrogen compound which contains as functional group(s) one or more OC=NH(y) groups, CH(x)-NH(y) groups and/or =C-NH(y) groups, the symbols y independently of one another having a value of 0, 1, 2 or 3 and x having a value of 1, 2 or 3, for example urea or melamine, diammonium hydrogen phosphate and/or ammonium dihydrogen phosphate; and an ammonium halide. Preparations of this type are advantageously used to render combustible materials such as textiles and wood products flame-retardant. Moreover, these preparations, especially in concentrated form, can act as extinguishing water.
Description
wo 90~l~9g 2 ~J 3.~ 7 ~.3~
': 1 .
Flame~retardant composltion, and use, Ihe invention relates to a rlame~retardant preparntion whlch contain~ ~mmonium phosphate und one or more nitrogen comPounds libersting ummonia on decomposltion.
A preparation of this type is disclo~ed in US Patent 3,390,019. More particularly, this US Patent relates to the treat-ment of wood fibre product~ with an aqueous solution Or a flame-retardant preparation which contains ammonium phosphate and in i which a decomposition inhibikor for the ammonium pho~phate is nl80 incorporated. A decomposition inhibitor Or this type i~ de~ined as a nitrogen compound which must decompose below the decomposition temperature of the ammonium phosphate (i.e. monoammonium phosphate or diammonium phosphate) with the liberstion Or a~nonia. ~oth inorganie nitrogen compounds, such as water-soluble ammonium salts, ~or example the am~onium halides, ~nmonium carbonate and ammoDium sulphide, and or~anic nitrogen compounds, such as amides and ~nidines, for example urea, formamide, acet~nide and guanine, are mentioned as examples of such decomposition inhibitors. The aim of the invention described in this US Patent 3,398,019 lies in the prevention or substantial minimilization Or the undesired dis-coloration of wood fibre products impregnated with the aqueous ammonium phosphate solution during the drying process for said pro~ucts, which process is ccrried out above the decomposltlon temperature of ammonium phosphate.
Differing from the abovementioned US Patent 3,398,019, the ai~ Or the inventlon is to develop a flame-retardant preparation which is both particularly efrectlve and can be applied in a simple manner to, or in some cases i~, the materials to be protected.
There is still a great need for a rlame-retardant preparation o~
; this type since the i~re hazard which is associated with the use Or i many combustible materials, such a5 ~textile materials, is - - ' appreciable and must in no way be underestimated, It has been found that the aim indicated above can be achiéved 1~ the preparation contslns at least ~ an srg~ic nltrogen compound which contalns as functional ' ' ;3 1 ~ . 5ri~E'r ~ ". ~. ,. ,..~ -_ ~
,~,, ,, ., ,,., .. ,... - - - .
': 1 .
Flame~retardant composltion, and use, Ihe invention relates to a rlame~retardant preparntion whlch contain~ ~mmonium phosphate und one or more nitrogen comPounds libersting ummonia on decomposltion.
A preparation of this type is disclo~ed in US Patent 3,390,019. More particularly, this US Patent relates to the treat-ment of wood fibre product~ with an aqueous solution Or a flame-retardant preparation which contains ammonium phosphate and in i which a decomposition inhibikor for the ammonium pho~phate is nl80 incorporated. A decomposition inhibitor Or this type i~ de~ined as a nitrogen compound which must decompose below the decomposition temperature of the ammonium phosphate (i.e. monoammonium phosphate or diammonium phosphate) with the liberstion Or a~nonia. ~oth inorganie nitrogen compounds, such as water-soluble ammonium salts, ~or example the am~onium halides, ~nmonium carbonate and ammoDium sulphide, and or~anic nitrogen compounds, such as amides and ~nidines, for example urea, formamide, acet~nide and guanine, are mentioned as examples of such decomposition inhibitors. The aim of the invention described in this US Patent 3,398,019 lies in the prevention or substantial minimilization Or the undesired dis-coloration of wood fibre products impregnated with the aqueous ammonium phosphate solution during the drying process for said pro~ucts, which process is ccrried out above the decomposltlon temperature of ammonium phosphate.
Differing from the abovementioned US Patent 3,398,019, the ai~ Or the inventlon is to develop a flame-retardant preparation which is both particularly efrectlve and can be applied in a simple manner to, or in some cases i~, the materials to be protected.
There is still a great need for a rlame-retardant preparation o~
; this type since the i~re hazard which is associated with the use Or i many combustible materials, such a5 ~textile materials, is - - ' appreciable and must in no way be underestimated, It has been found that the aim indicated above can be achiéved 1~ the preparation contslns at least ~ an srg~ic nltrogen compound which contalns as functional ' ' ;3 1 ~ . 5ri~E'r ~ ". ~. ,. ,..~ -_ ~
,~,, ,, ., ,,., .. ,... - - - .
2~5A7~ 2 ~^
group~s) one or more O~C-NH(y) groups, CH~x)-NH(y) groups and/or =C-NH~y) groups, the symbols y independently of one another having a value Or O, 1, 2 or 3 and x having B value ~r l, 2 or 3, - diam wnium hydrogen phosphate and/or ammonium dihydrogen phosphate: ~nd - an ammonium h~lide.
In connection with the sbove definition of the organic nitro-gen compound it is emphasized that the presence of a 0=C, CH(x) and/or =C group in the a-position relative to the nitrogen atom is essential since, ~urprisingly, lt has been found that, at high flame temperatures, compounds containing these types of groups can form radicsls which have a long life and are sble to react with oxygen. As fl conseguence, the extinguishing action of an ammonium phosphate-containing preparation according to the invention, the ammonium phosphate of which itself already has a flame-retardant sction, is promoted. Examples of Ruch nitrogen compounds are urea, dimethylurea, melamine, glycine, ~uanid.ine, guanylurea, acetamidine and formamide, of which melamine and, for reasons Or cost and av~ bility, especially urea are to be preferred.
When used on cellulose fibres, the more intensive flame-retardsnt action of the preparations according to the invention can, moreover, be ascribed in particular to the ~ormation of phos-phoric acid and phosphoric acid amides at elevsted tempersture, for example about 300 C, this being termed the phosphorus-nitrogen synergism within the rramework of the invention. At this tempera--ture and under these conditions an accelersted dehydration of -cellulose l~ obtained. During this dehydration the hydrogen i5 - withdrawn from the cellulose oolecule so that no compounds present- i ing a' ~ire hazard are able to form. The dehydration mechanism ; presumably procéeds via an acid protonation Or a hydroxyl group of the cellulose molecule. After the elimination Or water, which - --yiélds ~n intermedIate carbocatlon, a fairly non-hazardous elimin-stion product of the type >C~C< and a proton rorm. With this form 35 - of flame retardation it is essential thst thi~ mechanism takes ;
plsce at higher temperatures, while the prepflrstion according to the inventIon i~ neutral at lower temperature, such as during the ., , - Sl)E~STlFlJ~E: S~ET
, .. ........ ... . .... . .
W O 90/13699 PC~r/NL90/OOOGI
group~s) one or more O~C-NH(y) groups, CH~x)-NH(y) groups and/or =C-NH~y) groups, the symbols y independently of one another having a value Or O, 1, 2 or 3 and x having B value ~r l, 2 or 3, - diam wnium hydrogen phosphate and/or ammonium dihydrogen phosphate: ~nd - an ammonium h~lide.
In connection with the sbove definition of the organic nitro-gen compound it is emphasized that the presence of a 0=C, CH(x) and/or =C group in the a-position relative to the nitrogen atom is essential since, ~urprisingly, lt has been found that, at high flame temperatures, compounds containing these types of groups can form radicsls which have a long life and are sble to react with oxygen. As fl conseguence, the extinguishing action of an ammonium phosphate-containing preparation according to the invention, the ammonium phosphate of which itself already has a flame-retardant sction, is promoted. Examples of Ruch nitrogen compounds are urea, dimethylurea, melamine, glycine, ~uanid.ine, guanylurea, acetamidine and formamide, of which melamine and, for reasons Or cost and av~ bility, especially urea are to be preferred.
When used on cellulose fibres, the more intensive flame-retardsnt action of the preparations according to the invention can, moreover, be ascribed in particular to the ~ormation of phos-phoric acid and phosphoric acid amides at elevsted tempersture, for example about 300 C, this being termed the phosphorus-nitrogen synergism within the rramework of the invention. At this tempera--ture and under these conditions an accelersted dehydration of -cellulose l~ obtained. During this dehydration the hydrogen i5 - withdrawn from the cellulose oolecule so that no compounds present- i ing a' ~ire hazard are able to form. The dehydration mechanism ; presumably procéeds via an acid protonation Or a hydroxyl group of the cellulose molecule. After the elimination Or water, which - --yiélds ~n intermedIate carbocatlon, a fairly non-hazardous elimin-stion product of the type >C~C< and a proton rorm. With this form 35 - of flame retardation it is essential thst thi~ mechanism takes ;
plsce at higher temperatures, while the prepflrstion according to the inventIon i~ neutral at lower temperature, such as during the ., , - Sl)E~STlFlJ~E: S~ET
, .. ........ ... . .... . .
W O 90/13699 PC~r/NL90/OOOGI
3 2 ~ 7 .3 9 spplication thereof.
With regard to the third component of the preparation according to the invention, that is to say an ammonium hnlide such as ammonium chloride, ammonium bromide and ammonlum fluoride, lt is emphasized that ammonium hnlides generally decompo~e ~nto ammonia &nd ~he hydrogen halide gas at elevated temperature. These gaYes ~re diluted with the pyrolysis productq of the mater~al which has ~een treated with the prepar~tion ~ccording to the invention and ~ay itself be regarded a3 flame-ratardant. Moreover, in the presence of phosphorus compounds, compounds Or this type displny a synergistic effect with respect to the ~lame retsrdancy. This erfect, ~hich within the framework of the invention is termed phosphorus-h~logen synergism, can be explained by the formation of non-combustible phosphorus oxyhalides, which are able to react with the pyrolysis products of the treated material.
As can be derived from the above, the eminent fire-retardant action of the preparations according to the invention is based on a combination of ynergistic e~fects. t~ the basis of this it can even be proposed that relatively less isctive substance is needed to obtain a specific degree of flame-retardancy than would be needed with tbe separate active (= ~lame-retardant) materials. In this context it is pointed out that, for example, urea as such has no flame-retardant action but produce~a the synerglstic effect described above only in. the~presence c>f phosphates, that is to 5ay the action Or the mixture of phosphates and urea is greater than that of the separate components ~hemselves.
To return to the US Patent 3,398,019 discussed above, it can be/stated-that the speci~c combinstion of the three types Or substance of the preparations according to the invention is in no way u~ed in said patent; in other words, the eminent action o~ the preparations according to the invention bssed on the combination o~
the.synergi3tic efrects indicated above i8 in no wsy recognized in 7 ~! fiaidrUS patent Toisupport this statement~ rererénce is made to theclaims- o~ said US patent, ln~which only the combinatlon o~ two ~,-35, types of,substance Or the preparatlons according to the invention, that i8 to say ammonium pho~phate and an ammonium halide, is men-tioned. The Applicant is therefore Or the opinion that the ,~ ', - SUB~T~UT- S~EET
. .
W O 90/13699 PC~/NL90/00061 ~ 4~ 4 ~
invention must be regarded at least as an invention of choice with regard to the broad content of US Patent 3,398,019.
The invention relates in particular to flame-retardant preparations whi~l contain - ures and/or ~elanine, proferably urea, ~ the organlc nitrogen compound;
- a mixture of diammonlum hydrogen phosphate and ammonlum di-hydrogen phosphate; ~nd - ~mmonium chloride and/or ammonium bromide, preferably ammonium chloride, as the ammonium halide.
The respective amounts- of the three components preferably used in.the preparations according to the invention are advantage-ously - 2-5 parts by weight, preferably 3.5-5 parts by weight, of ures;
- 7.5-20 parts by weight, preferably 10-15 part~ by weight, of diammoniu~ hydrogen phosphate/ammonium dihydrogen phosphate, and - 0.25-0.75 part by weight, preferably 0.3-0.5 part by weight, of ~mmonium chloride.
. For applying the flame-retardant preparation according to the 20 invention to products to be rendered flame-retardant, the above-- mentionea three types of components are advantageously dissolved in .. . ..
an effective amount in water; the pH Isf ~uch a solution is in the range 6-ô. More particularly, the three- types of components are .. . . .
dissolved in the amounts indicated above in x. 100 parts by weight ' . 25 of water, x having a value ln the range 0.25-5.
Since some Or the abovementioned three typea Or components can also be formed in situ. when making up a water-containing ,. .... ... .
. preparation according.to the invention, it is''posaible in the case of a;;~preparation ;built up from urea, :diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride to use, in addition to urea, sultable amounts of ammonia, hydrogen chloride.and phosphoric acid. Preferably,` the three'lastmentioned reagents~ are.jused in the form. of-an aqueous''solution, such as t ammonia ~25 % solutlon), hydrochlorlc~ acid (30 X solution) and phosphoric acid ~85 X solution), In vlew Or the fact' that some of the. am00nla is lost by evaporatlon a~ a result Or the heat of . .
reaction generated, an appreciable proportion Or the required :: , - .-- SUB5TITUTE SH~E:T
... . . ... . ... . . .
W O 90/13699 PCr/NL90/OOOS1 5 2~7~
smount of di~mmonium hydrogen phosphate is added in the form of this compound. By this means, the undesired loss of ammonia is reduced, which leads to an appreciable saving in the required amount of ~mmonia.
There are numerous advantAges associated with the preparation according to the invention. Firstly it i~ pointed out thst the preparstion in guestion is uade up of substances which are non-toxic or are of very low toxicity, so that there can hardly be objection to the use thereof from the environmental standpoint.
Moreover, the preparation in questlon, as a solution in water, has a neutral pH, that i~ to say a pH in a range of 6-8, and can there-fore be regarded as non-irritant for the sk.in. ~ests carried out in accordance with OECD guidelines with a preparation made up of urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride have shown that a preparation Or th~s type is not irritant for the skin and eyes and is even considered non-tox$c when taken orally (in small amounts). To increase the ~dhesion between the active constituents of the flame retardant: preparation according to the invention and the materials or surfaces thereof to be treated, such ~ textile (fibres) and wood lfibres), an effective amount of glycerol can be added to the preparations in questio~. The amount of glycerol, to which there likewise can hardly be objection from the environm~ntal standpoint, to be used in the prepar~tion according to the invention i8, for e~ample, 0.5-1.5 parts by weight, preferably 0.7-1.0 part by weight, relative to the ranges indicated above w~th regard to the amounts - of the com-ponents to be used. Furthermore, when u~ed on textile fibres- and/or wood fibres, the preparation can be provided with a water-repellent agent so that the treated ribres acgulre a certain degree- Or water repellency and/or rastness to washing. As an example of an agent Or this type, the product "HYDROB FC" (Caldic Belgium N.V.,,Hemiksen, Belgium) can be used in an amount of, for . example, 3-5 % by weight, calculated relative to the matérial to be treated. For thi~ product, the manufacturer indicatés that on heating the materials treated herewith to, for example, 120 C or even 180 C the effect achieved, such as wat~r repellency, is f~st to washing.
SUg5 rlTU-rF SHEET
.... .. .. . . . . .
2 ~ 6 '~`
The preparation Or the rlame-retardant preparation~ according to the invention can t~ke place by simple mixing Or the components in a mixing vessel provided with a stirrer device. In v~ew of the reackivity o~ the products which may be used Qg starting materials, sucb BS ~le aboYementioned concentrated hydrochlorlc acld and concentrsted phosphoric ~cid, the ~xing vesael and the auxlliary apparatus belonging thereto are made Or corrosion-resistant material, such as stainless steel. The said components can be used as such, but usually are advantageously used as a solution in water. Specifically, hydrogen chloride, phosphoric acid and ammonia ~re used as solutions, which may be concentrated, in water, For this reason, concentrated hydrochloric acid (for example 30 % w/w), concentrated phosphoric acid (for example 85 % w/w) and ammonla ~for example 25 % w/w) are advantageously used in a practical embodiment of the production of specific preparations according to the invention. The mixing o~ the components usually takes place in a closed vessel.
The wster-containing flame-resistant preparations according to the invention usually contain 10-20 ~ by weight, advantageously 13-15 X by weight, of active substances. However, the preparations according to the invention can also exis;t in concentrated form, for example in connection with transport and for certain applications.
Examples of such applications are the production processes ~or paper and cardboard, the end products o~ which must h~ve a low final moisture content. In the latex inclustry also it ls considered desirable to work with concentrated sol~1tions as far a8 possible.
The flame-retardant preparations according to the lnvention can, as has already been stated in part, be used for many materials, such as textiles, paper, csrdboard,~wood and products derived thérerrom, and waterbased paint and slso as extinguishing material.
.
More particularly, diverse textile materials, such as cotton, cotton/polyester ,material, prererably contafning at- least 50 %
cotton ~i9 used as curtain material), wool, wool/cotton` woven fabric~, wool/visco~é woven rabrics, such as, ror example, 70/30 ~ wool/viscose woven fabric, which i9 used as upholstery material, - and also other textile materiAls may be mentioned. In order to .. SUi3S'r~TUTE SHEET
,, - .
W 0 90/13699 P Cr/NL90/0006l 7 i 2~7~9 render the textile materials flame-retardant it ~lready sufrices to ~oisten these once completely with the water-containin6 preparation according to the invention by, for example, lmmerslon or sprsying with an atomizer device. In this context It i8 import~nt that any 5finishes which ~ay be present on the textlle materlal ~re removed from the textile material beforehand. Aft0r moi~tening the textlle ~uterial with`the aqueous preparation ~ccording to the invention, this textile material may be force~dried if appropriate. The flame ret~rdancy Or the textile materials treated in this way, which are 10used, inter ~lia, as curtain or upholstery materials, is considered - to be ~ppreciable. Even on dry cleaning (that is to say cleaning without H20), the flame retardancy of the treated materials is virtually completely retained.
It is also possible to impart flame-retardant characteristics 15to diver~e types Or paper and cardboard using the preparations according to the invention. For this purpose the paper or cardboard is- completely moistened by ~eans of, for example, immersion or spraying, after whlch the material is dried.
Wood, ~iuch as deal, and products derived from wood, such as 20Triplex and chipboard, can also be rendered flame-resistant using a preparation according to the invention. Apart from by spraying or immer~ion, the preparation can be applied to porous wood materials, such as chipboard and the like, using ia brush, while the generally known ~acuum treatment is preferred for types of wood such as deal.
; 25Following on from the above, the prepar~tions according to the invention can be added to water-based paints, such as latex -paints, which are then applied to, for example, sheet materials.
~After applying a latex paint having a composition oP this type, and drying, a surface is obtained which is both rire-resistant and 30~esthetically pleasing.
Finally, the preparations according to the invention can be .used as such in the form of' an extinguishing aBent ror fighting : ,j J rires which are usually-fought-with water, such as in dwellings, wood fires and the like. In thé preparation accordin¢ to the 35invention which is used Q8 an extinguishlng ngent the relatlve amounts Or the componënt~ are advantQgeou~ly - 5-15 parts by welght, preferably 7.5-12.5 parts by we~ght, of , SUB5TIT.lJ.TE SHEE~ .
. .
W O 90/13699 PC~/Nl,~0/OnO6l ~2~4'~ 8 '~
urea or a similar compound;
- 15-40 psrts by weight, preferably 20-30 parts by weight, of a mixture of diammonium hydrogen phosphate and ammonium dihydrogen phosph~te; and 5- 0.5-1.5 parts by welght, preferably 0~6-1.0 part by welght, Or ~m~onium ~Lor~de.
The content of active subctances in the extinguishing water is advantageously very appreciable, for exnmple in the range 20-60 X by weight, preferably 30-50 X by weight. As a result of the 10particularly high extinguishing power of extinguishing water of this type, there is a possibility oP substantially restrictlng the water damage, which always occurs when extinguishing a rire in a dwelling or the iike. The multi-purpose nature of the extinguishing water indicated above can, moreover, be broadened ir a foam-forming 15agent, such as 8 suitable detergent, is aLso used ln the extinguishing water, in a concentration of, for example, 1-10 X by weight cslculated relative to the total composition of the exting-uishing water. This lastmentioned additive renders the said extinguishing water suitable for so-ca.Lled A-type fires (wood and 20paper fires) and B-type fires (liquid fires). A suitQble ~foam-forming agent is the commercially available product ~HCA Polar Newtonian" (a fluorocarbon compound) (Unlser, Amplepuis, France).
To summarize, it can be stated that the rlameretardnnt preparations according to the invention can be used in diverse 25 ? fields and for this reason constitute a particularly attractlve - ; product from the industrial standpoint.
The invention is illustrated in more detail with the aid of ~~ the examples below; these examples mu~t not be taken as restrictive.
_ ample I
3000 litres of water were fed lnto a stalnless steel mixing vessel which has a capacity Or 3800 litres and is provlded with a ';; stirrer devlce. The follow~ng were then ~dded independently of one ~ another ~ia separate storage ve~els~
`- 90 kg~oi urea ; Q - 195 kg of di~mmun$um hydrogen phosphate .
- 45 kg of ammonla ~200 litres o~ 25 ~ by weight ammonla) SU13STITU.TE~ SHEE~
.. . . .. .
2~7~'~
g - 24 kg of 30 % by weight hydrochloric acid ~21 litres), and - 150 kg Or 85 Z by weight phosphoric acld ~102 litres).
The amount of active constituents was 504 kg per 3000 litres or 16.B X by weight Or active sub~tances per unit volume Or preparation. The ~H o~ the flane-returdant prepsration obtained WQ9 abou~ 7.0-7.3.
Example II
3000 litres of water were fed lnto a stsinle~s steel mixing vessel which has a capacity Or 3800 litres and is provided with a stirrer device. The following are then added independently o f one another via separate storage vessels - 90 kg Or urea - 90 kg of ammonis (400 litres Or 25 X by ~eight ammonia) - 24 kg o~ 30 ~ by weight hydrochloric acid (21 litres), and ~ 3 kg of 85 % by weight phosphoric acid (~04 litres).
The amount of active substances in this case also was 504 kg per 3000 litres or 16.8 % by weight per unit volume of preparation. The pH of the flame-retardant agent was likewise between 7.0 and 7.3.
Example III
The procedure described in Example 1 was followed, except that 30 kg of glycerol were also added. A flame-retardant preparation with improved adhesion characteristlcs was obtained.
ExamDle IV
; The procedure described in Example II was followed, except ~, 25 that 30 kg Or glycerol were also added. In accordance with thls sxample also, a water-containing preparation was obt~lned which had improved adhesion characteristics with respect-to the materials to be treated.
Example V
In this example the results are given Or a study whlch was carried out,to determine the efrectiveness Or a treatment with the preparation Or Examplé I~on,the burning characteristics of textile ,. . . ..... . .
materials Or diverse composition on heating,briefly with'a small heat source. In this study tests were also carried out to determine ; 35 whether the fire-retardant action of ,the product was influencedwhen the treated material~ had undergone dry cleaning without the use of water.
UBSTITU~E SHEEr , . . ... . . . .
W O 90/13699 PC~/NL90/00061 2 ~ i 9 Twelve textile materials, which are listed in Table A below, were incl~ded in the study. Before treating the materials with the preparation of Example 1, these materials were washed in a washing machine with a conventional detergent in order to remove any rinishes which ~y be present and were then dried in a drying oven or stored over silica gel ln a desiccator. The pretreated materials were immersed in the water-containing preparation Or ~xample I and then centrifuged and dried. Some of the treated sample~ of all materisls were then dry cleaned once (without the use of water).
All textile msterials were then sub~ected to an e~ploratory examin-ation in accordance with NEN Standard 1722 ~Brandgedrag van textiel; bepaling van het al dan niet gemakkeli~k ontvlambaar zi~n en de verticale vlamsnelheid'van verticaal toegepast textiel"
- (~Burning characteristics of textiles;' determination of whether or not the material is readily inflammable and of the 'vertical flame speed of textiles used verticallyn) of October 1981 (2nd impression). Samples of each type of textile were subjected to the following tests:
a) after single clamping, the untreated textile material was tested by applying a flame for a contact time of 5 sec.
-- Because ~11 materials burned away fairly rapidly,'a test with a contact time Or 15 sec was no longer carried out, b) the materials treated with the preparation in Ex~mple I and the materials dry cleaned once were tested using a contact time of 5 and 15 sec;
c) to aimulate curtain pleating, the curtain materials 1 to 9 - - - inclusive, listed-in Table A, were also tested in three layers behind one another. The test pieces were always ' $gn~t~d at the ed~e (Section 6.3.2 of NEN 1722). ' The test re$ults are given ~n ~able A below. In addition to -, !, the- textile compo6ition,'-the times taken' ror the three cotton measuring threads~ to burn through in 'the 'tests according to - ~ NEN 172~ are noted'in'this tablé. ;
The'symbol - which occur~ in Table A indicates that the ~lame front did not reach the meaRuring thread.
;~; ,. SUB~;TITUl'E SHE:E~ j WO 90/13699 P(~/r`lL90/00063 11 2~7~
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~ ~- ~ o o o~ o o ~-~
j:,;SUB5TlTUTE SHE~
WO 90/13699 P(;-r/NL90/00061 .: 12 2~4 _ ll _ ~~ `~
ll ll ll ll ll ll ll , i l l l l , , l l l l , i "
, 11 ~ ll ll ll ll ll ,, l l ,,, , . ll ll ll ll ll ll 11 , _ ._ _ .~ .~ ~ ~ ~ ~ ~
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~-SUE3STiTUT SHE:E~
W O 90/l3699 P~T/NL90/00061 1~ 2~;A7~
As can be ~een from the results given ln Table A, in the un~reated state all textile materials tested burn away fairly rapidly. In an assessment as curtain material or material under tension in accord~nce with the appendix to NEN 1722 and after a complete test in accordance with thi~ specification, they would in all probability be designated "readily flammablen. Moreover, it can be deduced from this Tsble A that the treatæænt wlth the fla~e-retardant preparation of Example I had a favourable to highly ~Qvour~ble in~luence on the burning characteristics of all textile ~aterials tested. The textile materials treated wlth the preparation according to the invention did not continue to burn aftér the flame used ~or ignition was removed. In a complete test ln accord-ance with the Standard, these materials will therefore very probably be designated "not readily flammable" according to the appendix to NEN 1722.
All of the textile materials still showed no continuat~on of burning after a dry cleaning step had been carried out once. The burning characteristics of the curtain materials treated with the preparation of Example I was not found to be less favourable in pleats (tested by clamping three layers behind one another~ than on the material ~tretched flat; the same applies after one dry cleaning step.
To su~marize, it can be stated that the preparation according to the invention which has been used has a favourable influence on the burning characteristics of textile ~aterials which are made up for the greater part from natural fibres.
Example VI
In this example the results are given of a ~tudy which was carried out to determine the errectiveness Or a treatment with ths preparation of Example I on the burning characteristics of samples of deal in accordance with NEM 3883.
Samples with dimensions of Z90 x 1000 mm,and 290 x 290 m~
respectively and a thickness Or 18 mm were used, in the study. The samples were trested in two ways, that is to say:
a) immérsing some Or the deal samples for 5 min in the preparation '' 'according to Example I, and ,c ~,~x~
b) impregnating the other deal samples in a boiler (1 hour vacuum/2 hours under a pressure Or 8 bar wlth the preparation according to Example I).
5UE~5~1TUTE SHEET
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W O 90tl3699 PCT/NL90/0006 ~ ~ ~ 14 The a~oun~s t~ken up w~th methods (a) and (b) are listed in Tables B ~nd C below. The ~mounts Or preparation taken up are given in g and as g/m2 and as kg/~3.
TA~LE B j, No. Untrested Liquid taken up after immersion wt. (g) (g) kg/m3 g/m2 _________________________________~___________________~_ I
1 2325.9 68.5 13.i 118.1 2 2336.1 69.2 13-3 119.3 3 657-5 32.1 21.2 l90.B
With regard to the third component of the preparation according to the invention, that is to say an ammonium hnlide such as ammonium chloride, ammonium bromide and ammonlum fluoride, lt is emphasized that ammonium hnlides generally decompo~e ~nto ammonia &nd ~he hydrogen halide gas at elevated temperature. These gaYes ~re diluted with the pyrolysis productq of the mater~al which has ~een treated with the prepar~tion ~ccording to the invention and ~ay itself be regarded a3 flame-ratardant. Moreover, in the presence of phosphorus compounds, compounds Or this type displny a synergistic effect with respect to the ~lame retsrdancy. This erfect, ~hich within the framework of the invention is termed phosphorus-h~logen synergism, can be explained by the formation of non-combustible phosphorus oxyhalides, which are able to react with the pyrolysis products of the treated material.
As can be derived from the above, the eminent fire-retardant action of the preparations according to the invention is based on a combination of ynergistic e~fects. t~ the basis of this it can even be proposed that relatively less isctive substance is needed to obtain a specific degree of flame-retardancy than would be needed with tbe separate active (= ~lame-retardant) materials. In this context it is pointed out that, for example, urea as such has no flame-retardant action but produce~a the synerglstic effect described above only in. the~presence c>f phosphates, that is to 5ay the action Or the mixture of phosphates and urea is greater than that of the separate components ~hemselves.
To return to the US Patent 3,398,019 discussed above, it can be/stated-that the speci~c combinstion of the three types Or substance of the preparations according to the invention is in no way u~ed in said patent; in other words, the eminent action o~ the preparations according to the invention bssed on the combination o~
the.synergi3tic efrects indicated above i8 in no wsy recognized in 7 ~! fiaidrUS patent Toisupport this statement~ rererénce is made to theclaims- o~ said US patent, ln~which only the combinatlon o~ two ~,-35, types of,substance Or the preparatlons according to the invention, that i8 to say ammonium pho~phate and an ammonium halide, is men-tioned. The Applicant is therefore Or the opinion that the ,~ ', - SUB~T~UT- S~EET
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W O 90/13699 PC~/NL90/00061 ~ 4~ 4 ~
invention must be regarded at least as an invention of choice with regard to the broad content of US Patent 3,398,019.
The invention relates in particular to flame-retardant preparations whi~l contain - ures and/or ~elanine, proferably urea, ~ the organlc nitrogen compound;
- a mixture of diammonlum hydrogen phosphate and ammonlum di-hydrogen phosphate; ~nd - ~mmonium chloride and/or ammonium bromide, preferably ammonium chloride, as the ammonium halide.
The respective amounts- of the three components preferably used in.the preparations according to the invention are advantage-ously - 2-5 parts by weight, preferably 3.5-5 parts by weight, of ures;
- 7.5-20 parts by weight, preferably 10-15 part~ by weight, of diammoniu~ hydrogen phosphate/ammonium dihydrogen phosphate, and - 0.25-0.75 part by weight, preferably 0.3-0.5 part by weight, of ~mmonium chloride.
. For applying the flame-retardant preparation according to the 20 invention to products to be rendered flame-retardant, the above-- mentionea three types of components are advantageously dissolved in .. . ..
an effective amount in water; the pH Isf ~uch a solution is in the range 6-ô. More particularly, the three- types of components are .. . . .
dissolved in the amounts indicated above in x. 100 parts by weight ' . 25 of water, x having a value ln the range 0.25-5.
Since some Or the abovementioned three typea Or components can also be formed in situ. when making up a water-containing ,. .... ... .
. preparation according.to the invention, it is''posaible in the case of a;;~preparation ;built up from urea, :diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride to use, in addition to urea, sultable amounts of ammonia, hydrogen chloride.and phosphoric acid. Preferably,` the three'lastmentioned reagents~ are.jused in the form. of-an aqueous''solution, such as t ammonia ~25 % solutlon), hydrochlorlc~ acid (30 X solution) and phosphoric acid ~85 X solution), In vlew Or the fact' that some of the. am00nla is lost by evaporatlon a~ a result Or the heat of . .
reaction generated, an appreciable proportion Or the required :: , - .-- SUB5TITUTE SH~E:T
... . . ... . ... . . .
W O 90/13699 PCr/NL90/OOOS1 5 2~7~
smount of di~mmonium hydrogen phosphate is added in the form of this compound. By this means, the undesired loss of ammonia is reduced, which leads to an appreciable saving in the required amount of ~mmonia.
There are numerous advantAges associated with the preparation according to the invention. Firstly it i~ pointed out thst the preparstion in guestion is uade up of substances which are non-toxic or are of very low toxicity, so that there can hardly be objection to the use thereof from the environmental standpoint.
Moreover, the preparation in questlon, as a solution in water, has a neutral pH, that i~ to say a pH in a range of 6-8, and can there-fore be regarded as non-irritant for the sk.in. ~ests carried out in accordance with OECD guidelines with a preparation made up of urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride have shown that a preparation Or th~s type is not irritant for the skin and eyes and is even considered non-tox$c when taken orally (in small amounts). To increase the ~dhesion between the active constituents of the flame retardant: preparation according to the invention and the materials or surfaces thereof to be treated, such ~ textile (fibres) and wood lfibres), an effective amount of glycerol can be added to the preparations in questio~. The amount of glycerol, to which there likewise can hardly be objection from the environm~ntal standpoint, to be used in the prepar~tion according to the invention i8, for e~ample, 0.5-1.5 parts by weight, preferably 0.7-1.0 part by weight, relative to the ranges indicated above w~th regard to the amounts - of the com-ponents to be used. Furthermore, when u~ed on textile fibres- and/or wood fibres, the preparation can be provided with a water-repellent agent so that the treated ribres acgulre a certain degree- Or water repellency and/or rastness to washing. As an example of an agent Or this type, the product "HYDROB FC" (Caldic Belgium N.V.,,Hemiksen, Belgium) can be used in an amount of, for . example, 3-5 % by weight, calculated relative to the matérial to be treated. For thi~ product, the manufacturer indicatés that on heating the materials treated herewith to, for example, 120 C or even 180 C the effect achieved, such as wat~r repellency, is f~st to washing.
SUg5 rlTU-rF SHEET
.... .. .. . . . . .
2 ~ 6 '~`
The preparation Or the rlame-retardant preparation~ according to the invention can t~ke place by simple mixing Or the components in a mixing vessel provided with a stirrer device. In v~ew of the reackivity o~ the products which may be used Qg starting materials, sucb BS ~le aboYementioned concentrated hydrochlorlc acld and concentrsted phosphoric ~cid, the ~xing vesael and the auxlliary apparatus belonging thereto are made Or corrosion-resistant material, such as stainless steel. The said components can be used as such, but usually are advantageously used as a solution in water. Specifically, hydrogen chloride, phosphoric acid and ammonia ~re used as solutions, which may be concentrated, in water, For this reason, concentrated hydrochloric acid (for example 30 % w/w), concentrated phosphoric acid (for example 85 % w/w) and ammonla ~for example 25 % w/w) are advantageously used in a practical embodiment of the production of specific preparations according to the invention. The mixing o~ the components usually takes place in a closed vessel.
The wster-containing flame-resistant preparations according to the invention usually contain 10-20 ~ by weight, advantageously 13-15 X by weight, of active substances. However, the preparations according to the invention can also exis;t in concentrated form, for example in connection with transport and for certain applications.
Examples of such applications are the production processes ~or paper and cardboard, the end products o~ which must h~ve a low final moisture content. In the latex inclustry also it ls considered desirable to work with concentrated sol~1tions as far a8 possible.
The flame-retardant preparations according to the lnvention can, as has already been stated in part, be used for many materials, such as textiles, paper, csrdboard,~wood and products derived thérerrom, and waterbased paint and slso as extinguishing material.
.
More particularly, diverse textile materials, such as cotton, cotton/polyester ,material, prererably contafning at- least 50 %
cotton ~i9 used as curtain material), wool, wool/cotton` woven fabric~, wool/visco~é woven rabrics, such as, ror example, 70/30 ~ wool/viscose woven fabric, which i9 used as upholstery material, - and also other textile materiAls may be mentioned. In order to .. SUi3S'r~TUTE SHEET
,, - .
W 0 90/13699 P Cr/NL90/0006l 7 i 2~7~9 render the textile materials flame-retardant it ~lready sufrices to ~oisten these once completely with the water-containin6 preparation according to the invention by, for example, lmmerslon or sprsying with an atomizer device. In this context It i8 import~nt that any 5finishes which ~ay be present on the textlle materlal ~re removed from the textile material beforehand. Aft0r moi~tening the textlle ~uterial with`the aqueous preparation ~ccording to the invention, this textile material may be force~dried if appropriate. The flame ret~rdancy Or the textile materials treated in this way, which are 10used, inter ~lia, as curtain or upholstery materials, is considered - to be ~ppreciable. Even on dry cleaning (that is to say cleaning without H20), the flame retardancy of the treated materials is virtually completely retained.
It is also possible to impart flame-retardant characteristics 15to diver~e types Or paper and cardboard using the preparations according to the invention. For this purpose the paper or cardboard is- completely moistened by ~eans of, for example, immersion or spraying, after whlch the material is dried.
Wood, ~iuch as deal, and products derived from wood, such as 20Triplex and chipboard, can also be rendered flame-resistant using a preparation according to the invention. Apart from by spraying or immer~ion, the preparation can be applied to porous wood materials, such as chipboard and the like, using ia brush, while the generally known ~acuum treatment is preferred for types of wood such as deal.
; 25Following on from the above, the prepar~tions according to the invention can be added to water-based paints, such as latex -paints, which are then applied to, for example, sheet materials.
~After applying a latex paint having a composition oP this type, and drying, a surface is obtained which is both rire-resistant and 30~esthetically pleasing.
Finally, the preparations according to the invention can be .used as such in the form of' an extinguishing aBent ror fighting : ,j J rires which are usually-fought-with water, such as in dwellings, wood fires and the like. In thé preparation accordin¢ to the 35invention which is used Q8 an extinguishlng ngent the relatlve amounts Or the componënt~ are advantQgeou~ly - 5-15 parts by welght, preferably 7.5-12.5 parts by we~ght, of , SUB5TIT.lJ.TE SHEE~ .
. .
W O 90/13699 PC~/Nl,~0/OnO6l ~2~4'~ 8 '~
urea or a similar compound;
- 15-40 psrts by weight, preferably 20-30 parts by weight, of a mixture of diammonium hydrogen phosphate and ammonium dihydrogen phosph~te; and 5- 0.5-1.5 parts by welght, preferably 0~6-1.0 part by welght, Or ~m~onium ~Lor~de.
The content of active subctances in the extinguishing water is advantageously very appreciable, for exnmple in the range 20-60 X by weight, preferably 30-50 X by weight. As a result of the 10particularly high extinguishing power of extinguishing water of this type, there is a possibility oP substantially restrictlng the water damage, which always occurs when extinguishing a rire in a dwelling or the iike. The multi-purpose nature of the extinguishing water indicated above can, moreover, be broadened ir a foam-forming 15agent, such as 8 suitable detergent, is aLso used ln the extinguishing water, in a concentration of, for example, 1-10 X by weight cslculated relative to the total composition of the exting-uishing water. This lastmentioned additive renders the said extinguishing water suitable for so-ca.Lled A-type fires (wood and 20paper fires) and B-type fires (liquid fires). A suitQble ~foam-forming agent is the commercially available product ~HCA Polar Newtonian" (a fluorocarbon compound) (Unlser, Amplepuis, France).
To summarize, it can be stated that the rlameretardnnt preparations according to the invention can be used in diverse 25 ? fields and for this reason constitute a particularly attractlve - ; product from the industrial standpoint.
The invention is illustrated in more detail with the aid of ~~ the examples below; these examples mu~t not be taken as restrictive.
_ ample I
3000 litres of water were fed lnto a stalnless steel mixing vessel which has a capacity Or 3800 litres and is provlded with a ';; stirrer devlce. The follow~ng were then ~dded independently of one ~ another ~ia separate storage ve~els~
`- 90 kg~oi urea ; Q - 195 kg of di~mmun$um hydrogen phosphate .
- 45 kg of ammonla ~200 litres o~ 25 ~ by weight ammonla) SU13STITU.TE~ SHEE~
.. . . .. .
2~7~'~
g - 24 kg of 30 % by weight hydrochloric acid ~21 litres), and - 150 kg Or 85 Z by weight phosphoric acld ~102 litres).
The amount of active constituents was 504 kg per 3000 litres or 16.B X by weight Or active sub~tances per unit volume Or preparation. The ~H o~ the flane-returdant prepsration obtained WQ9 abou~ 7.0-7.3.
Example II
3000 litres of water were fed lnto a stsinle~s steel mixing vessel which has a capacity Or 3800 litres and is provided with a stirrer device. The following are then added independently o f one another via separate storage vessels - 90 kg Or urea - 90 kg of ammonis (400 litres Or 25 X by ~eight ammonia) - 24 kg o~ 30 ~ by weight hydrochloric acid (21 litres), and ~ 3 kg of 85 % by weight phosphoric acid (~04 litres).
The amount of active substances in this case also was 504 kg per 3000 litres or 16.8 % by weight per unit volume of preparation. The pH of the flame-retardant agent was likewise between 7.0 and 7.3.
Example III
The procedure described in Example 1 was followed, except that 30 kg of glycerol were also added. A flame-retardant preparation with improved adhesion characteristlcs was obtained.
ExamDle IV
; The procedure described in Example II was followed, except ~, 25 that 30 kg Or glycerol were also added. In accordance with thls sxample also, a water-containing preparation was obt~lned which had improved adhesion characteristics with respect-to the materials to be treated.
Example V
In this example the results are given Or a study whlch was carried out,to determine the efrectiveness Or a treatment with the preparation Or Examplé I~on,the burning characteristics of textile ,. . . ..... . .
materials Or diverse composition on heating,briefly with'a small heat source. In this study tests were also carried out to determine ; 35 whether the fire-retardant action of ,the product was influencedwhen the treated material~ had undergone dry cleaning without the use of water.
UBSTITU~E SHEEr , . . ... . . . .
W O 90/13699 PC~/NL90/00061 2 ~ i 9 Twelve textile materials, which are listed in Table A below, were incl~ded in the study. Before treating the materials with the preparation of Example 1, these materials were washed in a washing machine with a conventional detergent in order to remove any rinishes which ~y be present and were then dried in a drying oven or stored over silica gel ln a desiccator. The pretreated materials were immersed in the water-containing preparation Or ~xample I and then centrifuged and dried. Some of the treated sample~ of all materisls were then dry cleaned once (without the use of water).
All textile msterials were then sub~ected to an e~ploratory examin-ation in accordance with NEN Standard 1722 ~Brandgedrag van textiel; bepaling van het al dan niet gemakkeli~k ontvlambaar zi~n en de verticale vlamsnelheid'van verticaal toegepast textiel"
- (~Burning characteristics of textiles;' determination of whether or not the material is readily inflammable and of the 'vertical flame speed of textiles used verticallyn) of October 1981 (2nd impression). Samples of each type of textile were subjected to the following tests:
a) after single clamping, the untreated textile material was tested by applying a flame for a contact time of 5 sec.
-- Because ~11 materials burned away fairly rapidly,'a test with a contact time Or 15 sec was no longer carried out, b) the materials treated with the preparation in Ex~mple I and the materials dry cleaned once were tested using a contact time of 5 and 15 sec;
c) to aimulate curtain pleating, the curtain materials 1 to 9 - - - inclusive, listed-in Table A, were also tested in three layers behind one another. The test pieces were always ' $gn~t~d at the ed~e (Section 6.3.2 of NEN 1722). ' The test re$ults are given ~n ~able A below. In addition to -, !, the- textile compo6ition,'-the times taken' ror the three cotton measuring threads~ to burn through in 'the 'tests according to - ~ NEN 172~ are noted'in'this tablé. ;
The'symbol - which occur~ in Table A indicates that the ~lame front did not reach the meaRuring thread.
;~; ,. SUB~;TITUl'E SHE:E~ j WO 90/13699 P(~/r`lL90/00063 11 2~7~
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WO 90/13699 P(;-r/NL90/00061 .: 12 2~4 _ ll _ ~~ `~
ll ll ll ll ll ll ll , i l l l l , , l l l l , i "
, 11 ~ ll ll ll ll ll ,, l l ,,, , . ll ll ll ll ll ll 11 , _ ._ _ .~ .~ ~ ~ ~ ~ ~
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~-SUE3STiTUT SHE:E~
W O 90/l3699 P~T/NL90/00061 1~ 2~;A7~
As can be ~een from the results given ln Table A, in the un~reated state all textile materials tested burn away fairly rapidly. In an assessment as curtain material or material under tension in accord~nce with the appendix to NEN 1722 and after a complete test in accordance with thi~ specification, they would in all probability be designated "readily flammablen. Moreover, it can be deduced from this Tsble A that the treatæænt wlth the fla~e-retardant preparation of Example I had a favourable to highly ~Qvour~ble in~luence on the burning characteristics of all textile ~aterials tested. The textile materials treated wlth the preparation according to the invention did not continue to burn aftér the flame used ~or ignition was removed. In a complete test ln accord-ance with the Standard, these materials will therefore very probably be designated "not readily flammable" according to the appendix to NEN 1722.
All of the textile materials still showed no continuat~on of burning after a dry cleaning step had been carried out once. The burning characteristics of the curtain materials treated with the preparation of Example I was not found to be less favourable in pleats (tested by clamping three layers behind one another~ than on the material ~tretched flat; the same applies after one dry cleaning step.
To su~marize, it can be stated that the preparation according to the invention which has been used has a favourable influence on the burning characteristics of textile ~aterials which are made up for the greater part from natural fibres.
Example VI
In this example the results are given of a ~tudy which was carried out to determine the errectiveness Or a treatment with ths preparation of Example I on the burning characteristics of samples of deal in accordance with NEM 3883.
Samples with dimensions of Z90 x 1000 mm,and 290 x 290 m~
respectively and a thickness Or 18 mm were used, in the study. The samples were trested in two ways, that is to say:
a) immérsing some Or the deal samples for 5 min in the preparation '' 'according to Example I, and ,c ~,~x~
b) impregnating the other deal samples in a boiler (1 hour vacuum/2 hours under a pressure Or 8 bar wlth the preparation according to Example I).
5UE~5~1TUTE SHEET
..... . .. ... ..... .. .. . . . . . . . .. . ..
W O 90tl3699 PCT/NL90/0006 ~ ~ ~ 14 The a~oun~s t~ken up w~th methods (a) and (b) are listed in Tables B ~nd C below. The ~mounts Or preparation taken up are given in g and as g/m2 and as kg/~3.
TA~LE B j, No. Untrested Liquid taken up after immersion wt. (g) (g) kg/m3 g/m2 _________________________________~___________________~_ I
1 2325.9 68.5 13.i 118.1 2 2336.1 69.2 13-3 119.3 3 657-5 32.1 21.2 l90.B
4 713-7 31.8 21.0 lB9.1 5 718.6 31.4 20.7 186.7 6 705.0 30.1 19.9 179.0 7 708.2 30.1 19.9 179.0 8 691.9 31.8 21.0 189.1 Average 40.6 18.8 168.9 TABLE C
~ No. Untreated Liquid taken up on vacuum/pressure ; wt. (g) trestment ~g) kg/m3 g/m2 __________________________--_~----_----_------ -- -- :
1 2305.g 2075.7 397.6 3578.8 2 2284.1 2131.1 408.3 3674.3 3 638.0 606.4 400.5 3605.2 4 644.7 555.4 366.8 3302.0 640.4 491.6 324-7 2922.7 6 643.6' ` 511.6 337.9 3041.6 7 710.9 851.9 562.7 506~.8 8 684.8 433.5 286.3 2577.3 Average 957.1 385.6 3470.8 No-. 1-2 dimensions 290 x 1000 x 18 mm Others dimensions 290 x 290 x 18 mm ~'' Tests in respect-o~ the flame propagation and flame flash-over were carried out in accordance with NEN 3883 using the samples treated ~n the above manner and using untreated samples. The samples were assigned to the re~evant class category on the basis of thé results obtained.
,. . ,.. ,,,. . . ~ .:
, , .: ,-, ~, , I
,, I
5UE~5TllrUTE SHEET
.
WO 90~13699 PCr/NL90/00061 ~-. 15 2~759 ~ 1~
f ,~; SU3E3~;T!TUT~iHEE~T
wo 9Q/13699 2 ~ PCT/NL90/00061 It follows from the results glven in Table D above that the treatment with the preparation according to the invention le~ds to an appreciable improvement in the ~ire retardancy Or the deQl. The treatment Or deal using the vacuum/pressure method even led to an improve~nt fron NEN 3~3 Cla~s ~ ~untre~ted deal) to NEN 3883 Class 2.
- ~ SUBSTITUT SHE~
~ No. Untreated Liquid taken up on vacuum/pressure ; wt. (g) trestment ~g) kg/m3 g/m2 __________________________--_~----_----_------ -- -- :
1 2305.g 2075.7 397.6 3578.8 2 2284.1 2131.1 408.3 3674.3 3 638.0 606.4 400.5 3605.2 4 644.7 555.4 366.8 3302.0 640.4 491.6 324-7 2922.7 6 643.6' ` 511.6 337.9 3041.6 7 710.9 851.9 562.7 506~.8 8 684.8 433.5 286.3 2577.3 Average 957.1 385.6 3470.8 No-. 1-2 dimensions 290 x 1000 x 18 mm Others dimensions 290 x 290 x 18 mm ~'' Tests in respect-o~ the flame propagation and flame flash-over were carried out in accordance with NEN 3883 using the samples treated ~n the above manner and using untreated samples. The samples were assigned to the re~evant class category on the basis of thé results obtained.
,. . ,.. ,,,. . . ~ .:
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5UE~5TllrUTE SHEET
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WO 90~13699 PCr/NL90/00061 ~-. 15 2~759 ~ 1~
f ,~; SU3E3~;T!TUT~iHEE~T
wo 9Q/13699 2 ~ PCT/NL90/00061 It follows from the results glven in Table D above that the treatment with the preparation according to the invention le~ds to an appreciable improvement in the ~ire retardancy Or the deQl. The treatment Or deal using the vacuum/pressure method even led to an improve~nt fron NEN 3~3 Cla~s ~ ~untre~ted deal) to NEN 3883 Class 2.
- ~ SUBSTITUT SHE~
Claims (18)
1. Flame-retardant preparation which contains ammonium phosphate and one or more nitrogen compounds liberating ammonia on decomposition, characterized in that the preparation contains at least - an organic nitrogen compound which contains as functional group(s) one or more 0=C-NH(y) groups, CH(x)-NH(y) groups and/or =C-NH(y) groups, the symbols y independently of one another having a value of 0. 1, 2 or 3 and x having a value of 1, 2 or 3, - diammonium hydrogen phosphate and/or ammonium dihydrogen phosphate; and - an ammonium halide.
2. Flame-retardant preparation according to Claim 1, characterized in that the preparation contains - urea and/or melamine as the organic nitrogen compound;
- a mixture of diammonium hydrogen phosphate and ammonium dihydrogen phosphate; and - ammonium chloride and/or ammonium bromide as the ammonium halide.
- a mixture of diammonium hydrogen phosphate and ammonium dihydrogen phosphate; and - ammonium chloride and/or ammonium bromide as the ammonium halide.
3. Flame-retardant preparation according to Claim 1 or 2, characterized In that the preparation contains at least the components urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride.
4. Flame-retardant preparation according to Claim 3, characterized in that the preparation contains the components urea, diammonium hydrogen phospahate/ammonium dihydrogen phosphate and ammonium chloride in relative amounts of - 2-5 parts by weight of urea - 7.5-20 parts by weight of (di)ammonium dihydrogen phosphate, and - 0.25-0.75 part by weight of ammonium chloride.
5. Flame-retardant preparation according to Claim 4, characterized in that the preparation contains the components urea, diammonium hydrogen phosphate/ammonium dihydrogen phosphate and ammonium chloride in relative amounts of - 2.5-3.5 parts by weight of urea - 10-15 parts by weight of (di)ammonium (di)hydrogen phosphate, and - 0.3-0.5 part by weight of ammonium chloride.
6. Flame-retardant preparation according to one or more of Claims 1-5, characterized in that the preparation is dissolved in an effective amount in water, the pH of the water-containing preparation lying in the range 6-8.
7. Flame-retardant preparation accordlng to Claims 4 and 6, characterized in that the preparation is dissolved in x. 100 parts by weight of water, x having a value in the range 0.25-5.
8. Flame-retardant preparation according to Claims 5 and 6, characterized in that the preparation is dissolved in x. 100 parts by weight of water, x having a value in the range 0.25-5.
9. Flame-retardant preparation according to one or more of Claims 1-8, characterized in that the preparation also contains glycerol.
10. Flame-retardant preparation according to Claim 9, characterized in that the preparation also contains 0.5-1.5 parts by weight of glycerol.
11. Flame-retsrdant preparation according to Claim 10, characterized in that the preparat$on also conta$ns 0.7-1.0 part by weight of glycerol.
12. Method for rendering products flame-retardant, ohsracterized in that a flame-retardant preparation according to one or more of Claims 1-11 is applied to the product to be protected and this treated product is dried.
13. Product rendered flame-retardant and obtained in accordance with the method according to Claim 12.
14. Water-based paint, characterized ln that this paint contains an effectlve content of the flame-retardant preparation according to one or more of Claims 1-11.
15. Extinguishing agent, characterized in that this extinguishing agent contains an effective content of the flame-retardant preparation according to one or more of Claims 1-11.
16. Extinguishing agent according to Claim 15, characterized in that the extinguishing agent is a 20-60 % by weight solution in water of active constituents in relative amounts of - 5-15 parts by weight of urea;
- 15-40 parts by weight of (di)ammonium (di)hydrogen phosphate, and - 0.5-1.5 ports by weight of ammonium chloride.
- 15-40 parts by weight of (di)ammonium (di)hydrogen phosphate, and - 0.5-1.5 ports by weight of ammonium chloride.
17. Extinguishing agent according to Claim 16, characterized in that the extinguishing agent is a 30-50 % by weight solution in water of active constituents in relative amounts of - 7.5-12.5 parts by weight of urea;
- 20-30 parts by weight of (di)ammonium (di)hydrogen phosphate; and - 0.6-1.0 part by weight of ammonium chloride.
- 20-30 parts by weight of (di)ammonium (di)hydrogen phosphate; and - 0.6-1.0 part by weight of ammonium chloride.
18. Extinguishing agent according to one or more of Claims 15-17, characterized in that the extinguishing agent also contains a foam-forming gent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8901118A NL8901118A (en) | 1989-05-02 | 1989-05-02 | FLAME-RESISTANT PREPARATION, PROCESS FOR FLAMMING-PREPARING PRODUCTS WITH SUCH A PREPARATION AND THE FLAM-RESISTANT PRODUCTS. |
| NL8901118 | 1989-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2054759A1 true CA2054759A1 (en) | 1990-11-03 |
Family
ID=19854594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2054759 Abandoned CA2054759A1 (en) | 1989-05-02 | 1990-05-02 | Flame-retardant composition and use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0471786A1 (en) |
| AU (1) | AU5677390A (en) |
| CA (1) | CA2054759A1 (en) |
| FI (1) | FI915161A0 (en) |
| NL (1) | NL8901118A (en) |
| WO (1) | WO1990013699A2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225464A (en) * | 1992-04-02 | 1993-07-06 | Material Technologies & Sciences, Inc. | Intumescent coating and method of manufacture |
| GB2301122A (en) * | 1995-05-24 | 1996-11-27 | Cyril Glass | Flame retardant compositions |
| DE102006056661A1 (en) * | 2006-11-29 | 2008-06-05 | Union Marketing Gmbh | Flame retardant equipment, its manufacture, application to flammable products and use |
| EP3098259A1 (en) | 2012-04-24 | 2016-11-30 | Winnitex Limited | Formaldehyde-free flame retardant compositions and their use for manufacturing durable formaldehyde-free flame retardant cellulosic materials |
| BE1025604B1 (en) * | 2017-10-02 | 2019-04-29 | Uniteq Sa | Cylinder for fire extinguisher |
| CN116535633B (en) * | 2023-04-29 | 2024-08-23 | 中国科学院长春应用化学研究所 | Preparation method of phosphated polypropylene carbonate copolymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2225831A (en) * | 1935-03-13 | 1940-12-24 | Herz Walter | Fireproofing composition |
| GB819190A (en) * | 1957-06-20 | 1959-09-02 | Dow Chemical Co | Fire retardant coating composition |
| US3398019A (en) * | 1963-02-21 | 1968-08-20 | Monsanto Co | Method for fireproofing cellulosic material |
-
1989
- 1989-05-02 NL NL8901118A patent/NL8901118A/en not_active Application Discontinuation
-
1990
- 1990-05-02 WO PCT/NL1990/000061 patent/WO1990013699A2/en not_active Application Discontinuation
- 1990-05-02 EP EP19900908691 patent/EP0471786A1/en not_active Withdrawn
- 1990-05-02 CA CA 2054759 patent/CA2054759A1/en not_active Abandoned
- 1990-05-02 AU AU56773/90A patent/AU5677390A/en not_active Abandoned
-
1991
- 1991-11-01 FI FI915161A patent/FI915161A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990013699A2 (en) | 1990-11-15 |
| AU5677390A (en) | 1990-11-29 |
| FI915161A0 (en) | 1991-11-01 |
| WO1990013699A3 (en) | 1990-12-13 |
| NL8901118A (en) | 1990-12-03 |
| EP0471786A1 (en) | 1992-02-26 |
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