CA2062756A1 - Fireproofing agent and its use - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
The fire-proofing agent contains at least one dehydrogenizing agent. It also advantageously contains a carbohydrate or a starch as binder. The following may be used as the dehydrogenizing agent: phosphate salts, urea, boric acid, aluminum hydroxide, while carbohydrates or starches are used as binders. In addition to these fundamentally important and generally appointed components, propellant charges and stabilizers as well as other additives, as for, instance, binder additives or synergists, can also be contained in the fire-proofing agent according to the invention. The fire-proofing agent is basically applied by adding it to the material or product itself and by impregnation after-treatment of a raw material, semi-finished product.
Impregnation may take place, for instance, by an immersion procedure, or by spraying or brushing the fire-proofing agent onto the material to be treated. The specific composition of the fire-proofing agent can be varied in accordance with the intended application.

Description

8 516 474 5~74 E. D. SCHINDLER 12~24~91 13:25 P.02 XC~ SS

Translated fron~..G~rman Inter~a~e ~olding s~
Boulevsrd de Parolles 30 CH-l?OO Fr~ibourg A FIRE-P~OO~ AqENT ANp I~S USE

The present ~nvention concern~ a fire-proo~ing at~nt and it~ use. Fire-proof iB ~rowing in importance o~ing to the steadily incre~ing number of ~ynthetic, industri~lly produced raw ma~ri~l~ a~d products. Mnny pl~8tic8 di~play~, for cx~ple, outst~nding tech~icsl properties in a v~riety of ares~ ~nd ~re al80 much ~ore interestin~ in ter~ o~ ~rice than ~ny Alternative natural eubstance~. However, de~pite the~o con~ider~tion~ they cannot be usod in ~any relevant areas becs~se t~ey o~ten ~re un~ble to ~ost the pertinent snti-incendiary regul~tions. On the other hAnd, there are Also many natural subst~nces And product~ O~H, for oxa~ple, wood, fiber~, yarn, or textil~ whiah ~re in eur~ent u~e and who~ com~u~tib~ y or ~,om~u~tion prop~rti~ constit~t~ ~n i.m~n~e potentlal h~a~d . Th~ growing ~n~ety aw~rene~ ~f con~umer~ ~nd the mPre ~tringent ~ire protection re~ulstion~
pl~ce ever hi~her requirement~ with re8srd to the flsme-proofing of, say, ~ynthetic resin~. Sy~tems which require . . : . . ..

8 516 474 5374 E. D. S~HINDLER 12~24~91 13:25 P.83 2~75~

ftame-proof ing occupy a major place in the brosd ran8e o~
applicationK of polyurethane~. These include PUR fosms and ~pecial hard fe ~s for insulation in the co~stru~tlon ~ctor.

But fire-proo~in~ i~ also prescribed for block roams used, for example, in furniture or insulation, and ~or cast ~oam~

ror the automobile sector. In addltion, fabric coating~, adhe~ives, lack~, packing materi41, 4nd electric 8e~1in8 compounds are s4bject to ever ~ore ~tring~nt gtandards.

There are various ~ire~proo~ing agenta known the purpa~e o~

which iH to reduce the combustibility of rHw material~ or product~, or at lea6t to eliminate their most dsngerou~

proportie~, e~peciaJ.ly their most dAn~erou~ re~ction products in actuAl rires, ~ome o~ the known way~ to flame-proo~

poly~rethanes ~re, for ex~mple, the u~e of rad~oactlve compound~, usually chlorin~ted and phoaphorsted polyols wh~ch react witb i~ocyanate. The fire-proofing agent in the case iB a component of the ~ynthetl~ re~in, A f~rther pos~1~illty iB to add non-resctive ~lame inhibitor~, i,e., compo~nd~

containing fluid halo~ens and phosphorus. When hslo~en compounds and antimony trioxide are used, the araokin~ o~ the r~dial chain8 p~od~c~d by combustion i8 acaelorated in the 8s~ pha9e. The p~od~c~ o~ thi3 incomplete combustlon help con~idernbly to inten#if~ ~moke for~at~on- In hlghly cros~-linked syBtem~ ~uch a~ PUR hard ~oam, the tri~er~tion of isocyanate to i~ocysnate (PIR $oam~) can re0ult in a ~oo~
fire pcrformance. PUR ~oft foams sre inareasingly bein~

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,, ~ 516 474 5374 E. D. SCHINDLER 12~24~91 ~3:26 P.~4 zoe~?~s~
fire-proofed by ~ubsequent impregnation with appropriatelY
treated di~per~ion~.

Mo~t productH known a~ fire-prooiin~ or as fla~e-proo~ing agents have a ~alogen 4nd phosphorus bs~e ~nd ~re therefore toxic, Gonerally, apeaking C, CO, CO2, and ~20 ~re formed from the combu~tion o~ polymer~. In addition, bydrohalogens (HCl, ~Br) are ~or~ed ~ro~ conventional halogen-con~a1nin~ flame-proo~ing ~gents from antimony trioxide ~b20a) with the h~logen~ SbOCl and SbCl3. HCN i~
formed in addition to nitrogen oxides ~om nitrogen-containin~ fla~e-p~oofing a~entH~ Th~ conventional fl~me-proofing a8ent~ dimihish total oombustion to CO2 And H20 ~nd promote the formation o~ i.ncompletely oxidi~ed decomposition product~ a~, Eor example, C and ~0. The csrbon black thu~
formed increases th~ density o~ the smoke. Othor reaction products are hi~hly t4xic and corrosive, Thu8, the acid~
formed ~rom the burnin~ o~ haloBe~-containin~ or hnlo~en-~lame-proo~ed polymera are capable of cAu6ing ~econd~ry dama8e to, ~or ~xample, electrical or olectronlc egu~pm~nt of n maKnitude f~r ex~eoding the pri~ry d~maBe c~used by tho firo.

It i~ there~are the purpose o~ the pre~ent invention to produce a halogen-free, fire~proo~ing agent thst hau univorsal applic~bility, that an ~uch ig more e~ective thAn known aRent~, and in addition i~ not toxic.

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~ 516 474 5374 E. D. 5CHINDLER 12~24~91 13:26 P.05 2 ~ 5~
The Ai~ WA~ achieved with a ~ire-proo~in~ ~ent th~t contain~ at lea4t one dehydrogenizin~ agent.

The fir~-proo~inR a~ent propo~ed by the invention m4y al80 c~ntain othor components, e~pecially a carboh~drate or a ~tarch as binder. Tn ~ddition, it also appears to be advAntageou~ if it ~l~o c~ntains alulDinum hYdroxide. Th~
followin8 i8 A compilation or li~t with tho ~eneral headin~u o~ ~ix p~ible prinoipal component~ a~ ~cll ~bhcadin~u which theoretically can be Gompletely ~re~ly combined to ~oro a fire-proofin~ agent acco~din8 to the invention, ta~ing into uccount the minimal requi~ement that it contnin at lea~t one dohydro~enizin~ agent.

1. Pehydro~enizing a~ent l.t. Phosphate salt 1.1.1. Monopbo~phoric acid 1.1.2, Monoammonium hydrogen pho~phate I.1.3. Dia~moniu~ hydro~en phoHphate 1.1.4. ~rea phosphate 1.2. Urea 1.3. Boric acid 1.3. Aluoinum hydroxide 1.4. Aluminum Rul~ate-18 hydrate (~er~an Pbarn4~0poia 7) 2. Binder4 2.1. Carbobydrat~s 2.l.1. Mono~aacharide~
2.1.2. Pi~accharide~
2.1.3. Poly~accharide~
2.2.4. Starches . 2.2.4.1. Wax malt starch 2.2.4.2. Corn ~tarch 2.2.4.3. Wheat starch 2.2.4,4. Alu~inum hydroxide ~ 516 474 5374 E. D. SCHINDLER 12~24~1 13:26 P.~6 Z~5~75~

. Propell~nt CharBe~

3.1. M~lamine 3.2. Ammonium hydrogen carbonate 4. Stabilizing ayentx 4-~ ipenta-erythrite 4.2. Penta-erythrite 4.3. BorstoR
4.3.1. Borax . Binder additives 5.1. PVA copolymerizste ~.2. ~romine 5.3. Silicateo ~.4. Phosphates 5.5. Antimony ~ .

6.6. Am~oni~lm : .
6.7. Borium 5.8. H~lo~en~
5.9. Additives 6. Sy~rgist B

6.1. Dicumyl peroxide 6.2. Tetraphenylbutane 6.3, Tatrapbenylbutane hydrazine 6.4. ~orrocen 6.5. Dimethyl methylpho~Phonate IP~MP) The fi~e-proo~ing agen~ according to the in~ention iu applied in principle by adding lt direotly to th~ ~aterial or the product its~1f And by ~ub~oquont im~re~natlon treAtment of a ~AW mAteriBl~ semi-finished product~ or finished product. Impregnation ma~ take plaae, ~or ex~mple, via an immersion proeedure or by ~prayinR or brushin~ the ~ire-proo~inR agent onto ~he mAteriaI- Tbe ~pecific compa~ition of the fire-proofin8 ngent may be varied as a functi~n of ~he int.ended u~e. In principle, J a iire-proofin~ agent with ' .. . . . .
- ~ : , : . - . . ~ . . -., .. - ... . . - .

~ 516 474 5374 E. D. SCHINDLER ~2~4~9~ ~3:27 P.~7 2 ~ S~

compo~ition according to the invention can be sdded to any raw ~ateri~l a~ ~ filler snd the latt~r can then be treated &E~ UlilUBl with the effect that the r~w m~terial 80 treated will ultimately re~ult in a product ~hich i~ no longer co~bustible. The exaot ¢ompo~ition ror e~ch psrticular c~e will depend on the raw material or product to be trested, a~
~ell a~ on ~he particular type of application, for ex~mple, on whother the ~ire-prooPing 4gent i~ added diroctly to tho raw ~sterial or whether a finished product iB ~ub~equently troated with the rire-prooiing agent in nn i~pregnstion procedure .

The mo~t out~t~ndin8 advantage~ of the ~ire-proofing a~nt uccording to the invention are the followlnB:

the cAse of synthetic foam, ~eltln~ of the latter i8 prevented 4hould a fire ocour.

2. In synthetic foam, carbonization in abetted in caHe of fire, ~o that drippinx and tric~ling of the burnin~
m~terial i~ prevontod.

3. The ~oke den~l~y ln case o~ ~ire ln reduoed by the rire-proofing aBont accordinB to the inv~ntion.

. In ~ynthetic ~o~m, th~ buckling re~tAneo i~ af~ected only negligibly and the ten~ile strength, practically not at all, by the ~ire-proo~ing ngent.

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.- : . . :

~ 516 474 5374 E. D. SCHINDLER 12~24~91 13:27 P.08 2('~55 5. ~oam~ meeting the ~pecifications DIN ~10~, class Bl oan be produ~ed without proble~ when the fire-proof ln~ aKent -`.
~ccording to the invention i6 u~ed.

6. The ~ro~ den~ity o~ a ~ynthetic ~oam i~ incr~sed by sddition of the iire-proofing ~gent according to the invontion.

7. The ~ire-proo~in~ agent according to the invention ~eat~res bettor v~lue~ ~or the indiceK electric arc ro~istance, hardness, weather resi6tanco, and ~hoc~
re~i~tance a~ compared with other filler~

8. Add.i~ion of the ~ire-praa~ing agent accordin~ to the invention i~pr~ves the rheoloBical properties, i.e., the flow behavio~ o~ a eynthetic m~teri~l.

9. Bec~u~e of its polar charncter, the fire-prooYing a~ent according to the invention i~ readily dispersible in water.

10. Becauso of it8 physical and chemical prope~tie~ a hi~her filler content (up to 1000 pe~ hund~od re~n ~phr]) o~ the ~ire-proo~in~ a~ont acGording to the invontion i6 per~itted ~o th~t a corre~pondin~ly higher flamo-proofin8 i~ attainable, 11. The fir~-proofin~ a8en~ aacordin~ to tbe invontion i8 onvironmentAlly ~riendly a~ it i8 h~loxen-f~ee snd hence : .. . . . . ..................... . . . . . . . .

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~ 516 474 5374 E. D. SCHI~DLER 12~24~91 13:28 P.09 2~ 75~

not toxic.

12. The iire-proo~ing a8ent sccordin~ to the invention io also intere~ting in term~ of pri¢e a~ its costs are roughly half the cost~ of the raw materiAlK ucually used in ~oam~.

~specially advantageou~ ~pecific component~ and the~r co~bination to for~ a fire-proofin~ aRent a~cording to t~o invontion ~re e~idont fr~ tho dependent product claim~ The ~pec~al combination~ o~ the components are adapted to the particular mate~ial~ and products to be protected, a~ will be de~cribed in detail in t~e iollo~inK on the bAsis of examples .

A iirst i~portant application of the fire-proofin~ aRent according to the invention i~ flame-proo~ing o~ synthetic mat~riAls. To this end, the Yir~-proo~ing agent sdvant~geously oon~i~ts o~ a mixture o~ a dehydrogeni~in~
aKent, a binder, a propellent char~e, and a stabillzer.
Acoording to the invention, the dehydrogeni~inB Ago~t 1~

ureA, a known compound of carbon, hydrogen, nitro8en, ~nd ~xygen~ bu~ on tho o~h*r h~hd~ a phosphate ~slt, ~or exa~ple~
monopho~phori~ Acid, mon~ammaniu~ hydrogen pho~phate, diammonium hydro~en phosphate or urea pho~pbate, is used a~
well. The following are a~so ~uitable: boric acid, ~luminum hydroxides or, for ex8mple~ aluminum Bulfate-l8-hydrute~
according to the German Pharmaoopeia 7. Carbohydrate~ such 8 51~ 474 5374 E. D. S~HINDLER 12~24~91 13:28 P.~

2('~75~

as, for example, mono~Accharides, disaccharide4, or p~ly~acoh~rides or ~t~rche~ can be used a8 binder~. Mela~ine and a~monium hydro~en car~onate can be used au propellent -~
charge, while tripenta-erythrite, penta-erythrite or a borate are suitable a~ stabilizers. A fire-proofinR aBent with ~uch a aomposition i~ ~oam-forming, and i~ added to the stock ~olution adv~ntageously in a proportion o~ about 30X ~y weight. In principle, the $ire-proo~in8 agent can be up to 230X by weight, referred to the weight o~ the ~tock solution, witha~t a problem. ~oamin~ o~ the stock Molution contsining the added fire-proofing agent to form the final product must tak~ pl~c~ below tho re~ction temperat~re Or the ~ire-proofing agent, typically at temper~ture~ ~etween 150~C. and 200OC. Once the mixture ha~ hardened, the pores are clo~ed, 80 that the oxygen flow into the foamed m~teriAl i~ b~oken off, and the material as such i~ flame-proofed. Furth~rmore, later ~moldering in ca~e of tire i~ no lon~er po~sible, as the ins~lating layer thereby generated prevents the $ire gettinB to the m~terial and chokes off the in~lcw 4f oxygen-A proble~-freo, dif~ ntinted ~l~dlfi~ation o$ the rorm~l~ of the co~po~it$on i~ pn~sible to ~e~t the dir~orin~
speci$ication pro$iles o$ the v~riou~ products o$ the plastic~ industry. The basio components alway~ remain the Kame; only the specific composition in varied. In the particular ca~e, ~i~t~res o~ ~h* fire-proo~ing a8ent con~lst advantAgeously o~ aluminum hydroxide particle~, _g_ :

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~ 516 474 5374 E. D. SCHINDLER 12~24~91 1~: 29 P. ~ I

2~?5~7S~

carbohydrates, specifically, #accharides or another ~tarch, ~elamine, ammonium hydrogen carbonste, water, diAmmoniuw hydroKen phosphonate, with a few parts of the fini~bed product that i~ to be rire-proofed. The ~oa~-~ormin~
~dditive consi~ts o~ two binder~, sp~ci~ically sluminum hydrogen portion~ with starche~ or sa~charides, supported by ~ela~ine. Starch can be anion- o~ cation-~odified by ap~ropriate chemical reaction~. The production of ceramic ~iber ~haped part~ may ~e mentioned aH an example o~ the use of ~ ~Lion ~tarch. In thi~ production proc~4 the c~tion ~tarch iunction~ multifunctionally a~ a ~locculant, retention agent, and binder. The temperatures in drying equipment i~
80 high for ~ome ~tarch-bound pFoducts that ~pecial, particularly thermo~table ~tarches must be u~ed. Binders in many v~riations a~e possible. Therefore, ~tArch binder~ can al~o be adapted to the most diver~e condition~. In systems with low-water content, starches with, ~or example, a low water requirement, low water-retention capacity, a low ~elatinization point, buk a higher binding capacity, and hith tempor~turo re~t~nc~ and hi8h color ~autne~ ~re ~Bed~
Nativo ~nd modifi~d ao~n and wheat ~tarcheH moct th~e requirement~. In sddition, synergic ~ff~ct~ with regard to binding ~trenBth and effectivone~ ~a~ be achieved throu~b combinAtion~ or special modification_ oi the ~tarche~.
~indera modi~ied in this msnner Bre c~lled ~ystcm b~ndcr~;
they are harmonizod in ~ compo~ition agalnst the ti~erent -10- , .

~ 516 474 5374 E. D. SCHINDLER 12~24~91 13:29 P.12 X~?5~75~

specifiGation profile~ o~ the ~oqt diverse product~ an~
manuf~cturin~ tech~jque~. System binderH ach~eve the be~t indu~trial result~ bec~u~e they ~ake po~ible ~sxi~ bindin~
strengtbs in minimal quantities by dint o~ vAriou~ ~echanisms o~ action~ e.~.1 Htep-wiHe ~elati~;z~tion~ ~ni~l water re~uirement, and low drying e~ergy, partial migration (~and~ch effe~t), and, in the ca~e o~ cation properti*s, a hi~h $iber ar~inity~ The above-mentioned aritq~riA of choic~
make it pos6ible to choo~e the opti~al ~ta~ch binder additive to the fire-proofin8 ugent According to the invention ~or the mo~t diverse produc~ion processe~. The most import~nt criterion is total gelatinization, since only A c~mpletely gelatinized starch hs~ fully utili~ed All lt~ binder potential. Urea formaldehyde re~ins (UF), phencl re~inQ (PF
resols and novolacs) ~nd mel~mine re~in~ (~F) can be co~bined with o~pecially modified ~tarche~ over a brosd range of mix proportion~. The re~in ~olution i8 mixed with a ~OX st~rah ~u~pen~ion ~or u~e a~ a binder in the manufacture of prer~ed board, laminated bonrds, and boards of Ktone-fibor and Bln~
fiber. Diluted to the cuatomAr~ prAetlcal concentr~tion ~nd applied to the ~ub~trate, the ~t~rch opens up durin~
sub~e~uent oven drying, acquire~ film-formi~g pr~pertle and conden~e~ with the synthetic re~in to A holno~eneou~
film. Thi~ film exhibits a bu~klin8 re~istance ri~ing by more than 30X at ~n e~ch~nge r~te o~ about 50X, referred to the dry ~llb~tan~:e. The water re~i~tance o~ the ~il~ in .
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~ 516 474 5374 E. D. S~HINDLER ~2~24~91 13:3~ P.13 Z~ ~? 7 55 not reduced at a substitution of 30X, the Yil~ Ktability in 8 boiling water alternAtion t~t rem~ining unchanged up to a ~u~st~t~tlon rate o~ 15X o~ the dry resin referred to the dry ~tarch. Special carbonhydrate-ba~e system bi~dor~ in the fire-proofin~ agqnt. accordin8 to the invention can be t.Ailored to the prnd~ct to be protected and adapted to tho AppJi~ion profile of tbe indu~trial chemical and cer~mic indu~tries as far as total sul~ide wa~to liquor sub~titution.
To determine the stsrch content, the starch i8 red~cod to glucose by enzy~e or aGids. The choice of method dep~nd~ on the charucter and compo~ition of the ~ample. No toxi~
impairments occur.

All the hitherto mentioned raw material~ are toxically h~mle~s, with the exception o~ the pho~phate ~alts~ and are hitherto unknown a~ ~ire-proofing agent~ or additiv~s to fire-proofing agents. A flre-proofing agent with the given oo~po4ition ~herm~lly decompo~es only in an open ~la~e.
Ther~l deco~po~ition absor~s con~idera~le q~antities o~ ~eat which are thus ta~en ~rom the co~bustion ~roce~s Or the synthQtic materlal. Thi~ protects the ~ynthetic m~t~rial a~ain~t rapid thermal decompou1tion and thus ~top~ the formation of co~bustible products of decomposition. Ono product of decomposition iB steam, which ~Or~B an oxygen-r~pellent protective ~A~ around the ~ynthetic ~ater~al- The following recipe i~tr~ction~ ~re presented in tab~lar form for flame-proo~ing standard soYt ~oamH. The filler componen~
-lZ-.. . .. . . .
~: . . .. . . . . . . . . . . . .

~ 51~ 47~ 5374 E. D. SCHINDLER 12~24~91 13:30 P. 14 2~75~ :

is added to the polyol ~g ~ll other ad~itives. All fi8uFesre~arding the number of "part8 per~ re~er to part~ by weieht. The fir~-prooflng ~gent according to the ln~ention ~t~elf i~ referred to a~ the fill~r type ANTIFIXE 601 in the following. It con~ist~ o~, a~ong othcr things, aluminu~
oxide~ obtained with cau8tic soda ~ro~ the raw ~aterial bauxite, and th~n, mixed with carbohydrAte~ and 4t~rches, develop~ a ~ire-proofin~ effeat.

M~te~ial Y~riant 1 Variaat 2 Stand~rd polye~er polyol (branch~d, with ethylene-oxide-moditied polye~ter) 100 par~ 100 pa~ts Water 3.5 pnrt~ 3.5 part~
Tin II cataly~t 0.19 partH 0.19 psrt~

D~bco 33 LV .
Foa~ing oatalyst 0.12 part~ 0.12 p~rts Poly~iloxane xtabilizer 0.8 part~ :
Fire-proo~ing aBent (ANTIFI~E ~01) 20-30 part~

Cl-containing ahd P-containing polyol (13.5X P, 20X Cl) 20 psrt~
Tolnol diisooyanAte (TDI) 4~.2 part~ 44.2 part~

The above oompo~itions for A 80ft foam yield the ~ollow~ng qUantitAtiVe characteri~tics for the two varisnt~:
Chara~teri~t,ic~ Varian~ I V~rl~nt 2 Gro~ densi~y 4~
70 p~rts ANTIFI~E ~01about 36 ~bout ffO
Oxygen index 18 26 Xate of co~bu~tion MVSS ~0 0 - ~ -........... .. :

.

, ~
- ~, ~ 516 4~4 ~374 E. D. SCHINDLER 12~24~91 13:31 P.15 2(?~r_7S115 (MVSS iB a iire specifi~ation for ~otor vehicle ~pplication~) With ANTIFIaE 601 ~dded as a filler, the vi~co~ity ihcrease~.
However, this increa~e in vi~c08ity can be ~ub~tantially reduced by ~pecial additive~, e.8" dimethyl methylp~o~phonate (DMMP). ~nothe~ mothod ~or ~lsme-proo~ing o~ o~en-cell PU~ soft foams i~ a~ter-tre~tment in aqueou~
binder~ containin~ the fire-prooiing ~ent, Thi~ method avoid~ the problem of handling h;g~-vi~co~ity pol~ol di~per~ion~, but proteot~ the material only to a dep~h of penetra~ion of about 10-20 mm 4nd require~ the uYe of ~peclal machine~. nrying and cro~-linking of the binder cbo~ld t~ke place ~t temperature~ no higher than 2004C. wh~n the ~ire-prooiin~ ~ent i8 uBed ~ as oth~rwise the hydroxide und~r8Oe~
ther~al dec~position and the ~lamo proofing e~fect i~
reduced. However, cro~-linking oi the bind~r raises tbe attainable level of flame-proofing. The me~hanical properties o~ the foam can be altered a~ ~ ~unction of the binder ~nd the thickness o~ the coatin8. The i~pre~nation ~gent~ u~ed mu~t en~ure a good wetting o~ the io~m. Th~
depth of impre~nation OAn be incres~ed by ~u ~uch n~ sever~l centimeter~ by u~ing a ~uitable ~etting ~ent. For exs~ple, Cl~ Bl in ~N ~pecifications 410~ can be attained without problems ~or P~R roam when polychloroprene lattices sre u~ed ~or i~pre~nation. The 14~x i~ cro~-linked by a cu~t4nary procedure (8, ZnO, M~O). T~e ~ddition o~ a wetting nBent i~
recommended to e~f~ct a better di~per~ion. A foam thu~

.

~ 516 474 5374 E. D. SCH~NDLER 12~24~91 13:31 P.16 ;~?~75~

tr~Ated is eæpecially suited, for exa~ple, for upholstering ~sterial~. A~ an exllmple, the following i~ a recipe which give~ good ~ecb~nic~l pr~p~ties coupled with very ~ood flame resi~tAnce:

~ter~81 ProPortion Wnter 10 p~ts Ao~oniu~ acrylate di~persion ~gent 0.5 par~
ANTIFIRE 601 70 parts PVA~ (10%)** 6 part~ ~.
PVAC (60X)*** 20 pArt~

Source~:
*Additol XM-330, Hoech~t AG,, Germany $*Mewiol N 29-99, ~oechst AG, ~ermany ***Mowilith DC-20 F. ~oechst AG, Germany For a cold-hardened shaped foa~ with the following composition, ~or inMt~nce, an oxy~en index o$ 33X oxygen nnd A burn-up rate of 0 mm/g i8 determlned in accordance with MVSS 30 ~MVS~ is n co~bu~ti~h ~peci~ication for motor vehicle appl icat ion~

~t~rial, ProPort~on ANTIFIRE 601 60 part~

Sb~ 03 7 p~rts Cl ~$rom Cl-c~n~ainin~ flame-proofin~
a8ent 15 pArts The gro~s den~ity i~ 50-60 kg~3, the tensile stren~th i~

80-90 kPa, ela~ticity i8 about llOX ~t ~ ~r~kin8 stren~th of - - .
, ' ' ~

. .~ -~,: . .

~ 516 474 5374 E. D. SCHINDLER 12~24~91 13:32 P.17 X~ S~

about 200 N/m.

The ~ollowing recipe may be ~iven for a W~ ~h~ped roa~
~y~tem ror the auto~obile industry:

Msteris~ Pro~ortion High-~olecular-weight polyether polyol with prim~ry hydroxyl Broupg a~ :
compound with cnt~ly~t~ ~n4 water1~4 parts Cl-containinR snd P-containing polyol with 13.5X P and 20X Cl 10 pArt~
ANTIFI~E fiOl 70 pnrt~

Tolnol diisocyanste methylenephenyl diisocy~nate mixturo ~ T~I ~PI mixture) 45 partB

Thi~ foam hs~ an oxy~en index o~ about 30X oxygen according to MVSS 30 and the be~ conceivsble flame protection. Since working with normal h~gh-pre~ure ~achine~ i8 li~ited to a viscosity of ~bout 3 ~o 3.5 PBH (PA~Oa1 ffecond~ or higher visco~ities working up the mat~rial must tske place on filler mnchines, in the c~6e of thi~ recipe, a sli~ht separation of the polyol is evident ~fter 24 hours' ~tsndinK. However, no solid bottom sediment i~ produced. The Vi~CoBity CAII be further reduc~d ~hrough the addition of ~uitable Ad~ive~

The follo~ng r~cipe in suited ~or the ~anufActure ~r in~ ting fos~s, w~ich, ~or exsmpl~, can b~ u~ed as def]~cting wallQ in s~ort halls: :

~ 5~6 474 5374E. D. SCHINDLER 12~24~91 13:32 p.18 Z~ 756 Material ~ropo~t.. in Polyester foMm with . about 100 p~rtA
ANTIFIRE 601 100 part~
Ammonium polypho~phate 15 parts Br-P co~pound with 420X Br, 3.6X P 1~ parts Sb2O3 ~ part~
Zinc borate 6 part~

Thi~ foAm meets the ~pecificstion 4102, clas~ B1, and ha~ ~ :
gross den~ity o~ about 300 k~S.

ANTIFIRE 602 can al80 be treated without pro~le~s with polyurethahe adho~ivos. Suit~ble reGipes ~ust be wor~ed ou~
~or thi~ ror each area of application, ~ln¢e the adhesives mu~t ~eet certain ~pecific~tionx co~pounded with other m~rials rather than alone. In addition to the adhe4ive's aokual flAme protection, the thiaknesu o~ the coating and the compo~ition of the materials to be bound ~u~t ~l~o be t~ken into consideration, A guideline recipe i~ addition o~ 100 to 200 pArt~ ANTIFIRE 601 per polyol.

Polyurethane~ ~or Yabri~ coAtihg~ have better meohsnical properties than the often u~ed PVC, PiiYi~ulties due to ~i~ration of ~oftener cannot occu~ with thi~ material .
Should iir~ occur, no corro~3ive g&l8e8 are ~enerated, bt~t on the other hand the ~lame protectlon of these fabric coatin~
iB ~uch ~ore co~plicated than in thc caee of PVC ~ince itu halogen also give~ me pro~e~;tion for the polye~ter --lq--.......
..~ `!. ~....
, .. - ' - : ' ' . ' :

~ 516 474 5374 E. D. SCHINDLER 12~24~91 13:33 P. l9 2~?5?7S5 , f4bric. Witb a recipe o~, ~or example, about 70 p~rt~
ANTIFI~E and 10 part~ phosphoru8 and nitrogen-co~taining fla~e-prooPing agent~, oxy~en indice~ oi About 28% oxygen can be attained ln co~tings, without the addition of corrosive and toxic products. The oxygen index in the compound i~ reduced to About 18X ox~gen by coating the readily fl~m~able po~yester fabric. Thl8 le~el ic ~u~icient to ~chieve the DIN 4102, class ~1 cla~ ication. Flame-proofing in accordance with DIN 75200 (Ger~an industry fire ~peci f io4tion f~r motor vehicle ~pplications) i~ Bl~0 possible with this recipe. Solvent-containing ~;n~le componentff a~, for example, polyurethane lack~, and two-component coatinBff, can al80 be made rla~e-proof ~ith ANTI~I~E 602. An i~portant area of application here in, for example, w~ter-proof varnishing and flame-proofin~ of fine-pore PU~ foam~. Becau6e very hiRh filler concentr~tion~
c~nnot be ~ed ih ~he~e ca~e~, additional flame-proo$ing agent~ ~uch ~g ~l-contsining ~d Br~containing compound~, au well a8 the additiop of PVC powder~ sre uometlme~ nec~eu~ary.
The recipe~ csn be varied dependin~ on the foam to obtain an optimal bond. These materials are very weather-re~i~t~nt and are therefore suited for outside uffe a~, for example~ for roof PUR ~eAlin~ compouhd~, for cable in~ul~tion~, for tbe ca~ting of con~truction elementu. In ~ddition, they have a hi~h current-~low re~i~tance and resistsnce to he~t deformation. For open-air insulators~ a good weather .: - : . : ., . : . :. .... . .
.
. . . - -. ' - . - . ~ - ~ ' ~; 516 474 5374 E. D. SCHINDLER 12~24~91 13:33 P.2~1 75~
resistance i~ obtained throu~h the use o~ cyolo-aliphA~ic polyurethane~, ~hich u~like EP-resinM are ~e~i~tant to hydrolysi~, ANTJFIRE 601 impart# to the~e ~at2rials a ~ood electrl~ ~rc re~i~tance and re~i~t~nce to sur~ace ourrent leskage, a~ well a~ a hi~h-tenuion arc re~i~tance and ~
corre~ponding ~ood dielectric ~trength, in addition to a good flame re~istance. ANTIFIRE i~ especially super;or to all oth~r filler~ ~ regard~ ar~ tarlce. The use of a ~ n0d produc~ produces a good bond and hence a better stability in water and a better dielectric re~i~t~nce in a ~tanding time te~t. Since very hi~h concentration~ of fillers (about 70% of the total quantity) are u~uall~ u~ed, it i~ recommended that ~ mixturo of ~hree component~ ~e used, as this in optimal a~ re~ard~ vi~cosity and ~edimentation behavior. A three-component mixture oon~i~ting oi 400 psrts ANTIFIRE i~ advantageous. Visco~ities of about 70 P~K for 60 hours' ~tandin~ of the mixtu~ Are achie~ed without ~edimen~iotl ~ an additional ~our parts æilane Rre u~ed in cyclonliphatic~, In thi~ c~e, the ~iller i~ p~e-drled with ~eolitn pa~te sdded to the isooyanste, while polyol i~ added a~ a hardenin~ sgent.

' ~ .

' :
, ~ 516 474 5374 E. D. SCHINDLER 12~24~91 13:34 P.21 ;~?5~ ~ 5S

One recipe, for instance, con~istfi of:

Nu~erial Pro~ortion I~ocyanate (Baymidur VP KL 3-5001.) 100 pBFt8 Polyol (Bayg~l ~P KU 6698)50 parts ANTIFIRE 601 component6 300 pa~t~
~chieve~, for example, the ~ollowin~
VAlue~
Resistance to heat de~ormation, M~rtcns te~t: about 138~C.

Buckling re~istance About 96 MPa (MPB = N/~q.mm2 ) Arc resi~tance About 400 ~ec.
Oxyg¢n index About 32X oxygen `

Hardnes~, buckling resistance, and ~hock resi~tance can al~o be hei8htened by addition of alu~inu~ hydroxide ~Al~O~).

Thc following recipe in~tructian~ ~or ~lsme-proofing o~
poly~rethane hard foams are pre~e~ted in tabular ~or~. Tbe filler component i~ add~d to the polyo1 like ~ll other additive~. .
Material Vnriant StandArd polyetherer polyol (brsnched, polyether modifi~d with ethylcne o~ide) 100 p~rt~
Fri~en ll S l0 part~ ~:
Silicon oil 1.76 part~
Dabco 33 I.V ca~aly~t* l.18 part~
Ter~ethylene butaamidiamine (TMBDA) ~.51 part~ :
ANTIFI~E 601 0-200 psrtc I~ocyanate lMDI) 133 parts *obtuinable ~ro~ ~ond~r or Air Products ~ 516 474 5374E. D. SCHINDLER 12/24~91 13:34 P.22 .
2~ ?7S5 M~te r ial Ygli~L__~
Volanol ~N 49P 100 parts ~egostAR B 10~8 1 part ~CHA 3.6 part~
K 11 3.~ part~
ANTIFI~E 60l X, Y part~
(dimethyl~ethyl ph~phonate)(~MMO~
VorAntate M 2fi9 . 130 part~

In the cn~e of fire, the heat generated i3 lar8ely absorbed by the decomposition of ANTI~IRE 601 and, hence, t~ken out of the ~ynthetic materia1 co~bu~tion proce~s. The ~ynthetic ~aterial i~ protected a8ainst rapid thermal decomposition and the formation of com~ustible deco~position products i~ ~topped. The steam ~nerated by decomposit~on ~ormff an exy~en-repellent protective gax. A layer preventing the continu~tion of combu~tion ~or~s from the carbonisation products on the cur~a~e of the ~ynthetic ~sterial. A wei~ht per unit volume of 100-200 kg/m~ i~ 4chieved by virtue of the low Frygen proportion. Both polyol and i~ocyanate are mixed togOEther with th~ indicated qu4ntiti~s of ANTIFIRE 601 in 4rder to treat the larg~ ~mo~nt o~ filler. Di~ethyl methyl pho~phonate ~MMP) is u~ed aH a hi~hly Huitable synergi~t for ANTIFIRE ~01. For treatment, ANTIFIRE 601~ ~
well a~ other additive~ are added a~ ~uch a~ po~sible only to the polyol cemponent. Every addition o~ ~iller cau~e~ a ri8e in the visco~ity o~ tbe polyol. ~n the other h4nd, DMMP h~s .^ ;, -., 8 516 47~ 5374 E. D. SCHINDLER 12~24~91 13:34 P.23 2~ 5~

vi6co~ity-reducin~ effect which si~plifi~s trestment o~
the ~xtures. Oe~pite the addition of DHMP, ANTIFIRE 601 bri~g~ about a good education in the ~moke denaity in c~e o~ fire. Since the flame-proofin~ efiect o~ ANTIFIR~ ~01 i~
based, among other ~hingH, on the cir~-~m~ance that a protoct~ve layer o~ carboni~ation products ~rotect~ the synthetic materisl a~ain~t ~urther deco~po~ition, in the cnse of polYurethane~ it work~ be~t in 8y8tem~ which ~bet the for~ation of a closed protective layer by virtue oi pro~ounced carbonization e~iects. Hard roams ~how a relstively good carbonisation compared with otber PU~
ingredients becau~e o~ their r~latively high level of cros~-linking. Trimeri~ation of the i~ocyanate c~ponent yieldY
ev~n ~ore highly eros~-linkod PI~ foam~, ~hich have a very goo~ fire perfor~ance but, tec~nically1 are difficult and expen~ive t~ produce. There~orn, in pr~ctice, there i~ ~
growing tendency to ~witch to mix~d PUR-PIR foam~ produced by partial trimerization; the~e are calle~ PUI~ ~oa~a and combine the good fire per~ormance of PI~ foam~ with the ea8e o~ handlin~ of PUR ~oam~. By addition o~ 90 parts ANTIFIRE
601 and ten part~ DMMP, tbe proportion oi trimeri8ed i~ocyanate can be reduced to obtain an inoxpe~ive ~lame protection.

Polyol and ANTIF~RE ~01 can be mixed together with agitator~ and hjgh-~hearin~ ~tren~th or ~i~h ma~ticators.
Variation of the re~ction times w~en adding ~iller i8 of -22- ;

: ~., , , , - . : .. ..

- :, . . ~ .

- : ~ . . ~ . ..

.: . .. .

~ 5~6 474 5374 E. D. SCHINDLER 12~24~91 13:35 P.24 _~ .

;~ C. ~ir_ ~ S~i m~jor importance for the produGtio~ proceK~. The ~tarting tim~ enerally the same while the adh~ e free ti~e and the incre~ental time for adding 50 p4rts ANTIFI~ 601 to polyurethane i8 increa~ed by about 20%. The weig~t per unit volume of the foam incres~es owin~ to th~ greater density of the filler, n~mely, by a fActor of one to fiv~-fold, ~or AN~IFI~ 601 with 37 phr. The pcre ~t~ucture i~ also ~ htly altered by a change in re~ction ti~. The weight per unit volume i~ based on polyol re~erred to the ANTIFIRE
601 concentration.

The heat conductivity o$ PUR hard $osm~ is the most important criterion for use in the building uector. The heat conductivity referred to PU~ vsries only s~ightly with the addition o~ up to 100 parts ANTIFIRE 601. A preHsure te~t o~
hard foam~ ~hows incre~s~d hardne~s and brittl~ne~ with increase in the ANTIF~RE 601 content.

The E-module (N/~mZ) can be redu~od by addition to DMMP
a~ a ~oftener. Thi~ effect is e~pecially pronounced At hlgh ANTIFI~E 601 content.

The buckling resistance is only slightly dependen~ on the A~TIFI~E 601 content. The tensile ~tren~th iB not changed ~y addit~on of ANTIFI~E fiO1. The addition of about lX rhizinus ail re~erred t,o the proportion of fillsr msy be recommended to reduce the weiRh~ per unit volume.

~., ' ' . . , ~ 516 474 5374 E. D. SCHINDLER IZ~:~4~Yl 1~:35 P.2S

2~?, 55 I~ there must be no po~ibility of a PU~ ~oam being ~et srire by generally acces~ible source~ o~ ignition, nor ~ny possibility of meltin~ or o~ trioklinB or dripping oi burninR
substsnce, two nltern~tives ar~ recom~ended:

1. A ~oam with modified polyol8 and ANTIFI~ 601 ca~ be used, or 2. A hydrophilic foam with a very hi~h content of A~TIFIRE
601 can be u~d-The fir~t c~se ~e~ polyol8 (PHD) with pol~ureadi~per~ions which forw a ~olid crust and do not drip in a fire. Thi~ tendency toward crust formation i~ reiniorced much ~ore by the additio~ of from 70 to lZ0 parts ANTIFI~E
601 and the re~ult is a ~oa~ with no combu~tion effect.
Also, about 7X Cl ~nd 7% P can be uued a~ additives.

In the ~econd caHe, a foam based on the ¢onver~ion of a polymer i~ u~ed. An ox~gen index of 55X can be achieved with ANTIFI~ 601.. The filler i~ added to the i~ooyanate. The mechanical propertie~ can be variod over a wi~e rsn~e by v~rying the additives.

A $urther ~pplication of the fire-pro~iin~ 4~ent accordin~ to the invention i~ the $1ame-prooiin~ o~ wood, textile, paper~, and cArdboard, but al~o cBrpet~ ~ ~ilm8 ~
pulp, cellulose, and s~milnr products. For such applications th~ fire-praoring agent conQi~ts of ~t le~st one pho6ph~t~

8 516 474 5374 E. D. SCHINDLER 12~24~91 13:36 P.2~
, . .

21. Jr_ ~ 5 salt as a dehydrogenizing ag0nt and at leaBt one carbohydrateas a binder, as well a~ bor~tes if neoded; it is u~ed a~ an i~pregnation n8ent for th~ end t~eat~ent.

Three specis1 mixture~ have pro~en to be advant~geous:

l. UreA ~nopho~ph~ric acid a~ a dehydrogeni~ing ~gent, a poly~accharide, or a wax malt st~rch a~6 binder, a8 well ~3 borax as a 6tabilizer.

2. Diam~oniu~ hydrogen phosphate and boric acid aff ~
dehydrogeni~in~ a~ent, as ~ell a~ a polysaccharide or another carboh~drate ~g a binder.

3, ~ono~mmonium hydrogen pho~p~ate ~nd urea pho~ph~te as a dehydrogenizi~g a~ent, R po1ysaccharide or another c~rbohydrate as binder, a~ well as borax ~ ~tabilizer.

The tollowing is ~n eapecially ~uited ~ixture:

Naterial Proportion ~iammoniu~ h~drogen phosphate 20 part~
Urea pho~ph~te 20 psrt~
~orsx 10 part~
StArch l2 parts Water ~idual amount~

A fire-proofing agent accordin8 to the invention of this type will herein~ter ~e csl1et ~NTI~I~E 501. The deco~position o~ the fi~e-p~oo~in~ agent ANTI~IRE ~01 at .
, . .
: .
.
':' '. ' :
. ~: . ; .
: .. . ; , . . .

~ 516 474 5~74 E. D. SCHINDLER 12~24~91 13:36 P.27 ~,?~5~

temperatures above it~ reACtiOn te~perature produces lnertgasec which prevent acces~ of oxy~en. Further, the t~eatcd sub~tance i~ made ~lame-re~istant by virtue of the fact th~
at the hi8h combustion temperature~ dehydrog~nation i~
l"it1ated in it~ combu~tible co~ponent~ . Materialc treated with the fire-proofinR agent according to the invention ANTIFIRE 501, ~herefore, do not burn or are extin~ui~had by the~elve~ i~mediately arter the i8nitinB flame i~ rem~vod.
Even subsequent ~molderin~ i~ not po~ible since no oxygen can get to the materia]. ~he ~aterials are treated with ths fire-proofing agent ~N~ 501 by spraying the latter on 1.he ~aterial or by i~pre~nation immersion of the ma~$rial in the rire-proo~ing s~ent ANTIFIRE 501. The quantitative determination oi' the content of the flame-inhibiting ingredient tak~ plac~ a~ter the treated msterial iB dried, by measurinR tho increa~e in it~ wei~ht. Becauce the feel of the mater;Al i~ ~e~t al~ost una~fected by the treatment, the ~ire-proofing agent according to the invention~ A~TIFIRE
501, can also be u~d in the cellulose and pulp indu~try. A
high co~patibility with ~Ahy ma~erials i9 achieved by virtue of ~he binder ncco~panyin~ the ~ire-proo~ing sgent.

The fire-proofin~ agent accarding to the invention fe~ture~ precisely de~ined quality chsr~cteri~tic~ ~uch a~
purity, constant distribution, low relative water cont~n~, low electrolyte oontent, and a defined, BpCCifiC 6urface.

.. . .. . . . ..
. ~ , ~' ,' . . :',, .. ' : , , ."' ' '~
:' ' ~
~ : . ' ' ~ ' ~ 516 47~ 5374 E. D. SCHINDLER 12~24~91 13:37 P.28 .
r~ 5 ~

Special ~urface-treatin~ ANTIFIR~ 501-type~ make possible ea~y 4pplicstion and workin~-in. In addition, ANTIFIKE can also i~prove the machininK proce~s, and e~pecially the rheological propertie~ (flow behavior), 4nd h~ a po~itive il~tluence ~n the mechanical propertie~ o~ the tinal product. In addition to the AN~IFIRE product, distingui~hed ~8 a ha10gen-f'ree, non-corrosive ~nd physiologic~lly ~a~ flame-proo~in~ agent~ special aluminum hydroxide~ can be u~ed in the cardboard and paper indu~try aB
paint pig~ents and ~illers.

-

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A fire-proofing agent that contains at least one dehydrogenizing agent and a carbohydrate or a starch as binder.

2. A fire-proofing agent according to the preceding claim, which contains aluminum hydroxide.

3. A fire-proofing agent according to one of the preceding claims, which contains at least one phosphate salt as a dehydrogenizing agent.

4. A fire-proofing agent according to one of the preceding claims that contains aluminum-18-hydrate DAB 7 as a dehydrogenizing agent.

5. A fire-proofing agent according to one of the preceding claims, which contains mono-ammonium hydrogen phosphate and urea phosphate as phosphate salt.

6. A fire-proofing agent according to one of the preceding claims, which contains at least one borate.

7. A fire-proofing agent according to one of the preceding claim, which contains urea monophosphoric acid as phosphate salt, borax as borate, and a polysaccharide as carbohydrate or wax malt starch as starch.

8. A fire-proofing agent according to one of the preceding claims, which contains diammonium hydrogen phosphate as phosphate salt, boric acid as borate, and a polysaccharide or any other carbohydrate.

9. A fire-proofing agent according to one of the preceding claims, which contains a monosaccharide, disaccharide, and/or polysaccharide as carbohydrate.

10. A fire-proofing agent according to one of the preceding claims, which contains in addition a propellent charge and/or a stabilizer.

11. A fire-proofing agent according to Claim 10, in which melamine and/or ammonium hydrogen carbonate is the propellent charge, tripenta-erythrtite and/or penta-erytahrite is the stabilizer, and urea and/or mono-ammonium hydrogen phosphate and/or diammonium hydrogen phosphate is the dyhydrogenizing agent.

12. Use of the fire-proofing agent according to the preceding claims to be worked into raw materials and products by adding it as a filler or by subsequent impregnation of raw materials and products through immersion, coating, spraying or brushing on.

13. Use of the fire-proofing agent according to claims 1 through 11 for adding to plastics, and especially polyurethanes, as filler.