Патент USA US3077467код для вставки
c 3,977,458 Patented Feb, 12, 1963 3 2 pletely or partially neutralised with ammonia or a lower 3,077,458 NQN-AQUE?Ud FIRE RETARDANT ‘CQMPGSKTEUN CGMPRIMNG A UREA FGRMALDEHYDE CON _DENSATE . , . Gerrit Queiie, Amsterdam, Netherlands, and Cyril Aubrey Red-Earn, London, and Raymond Thompson, East Molesey, England, assignors, by mesne assignments, to Alirn (Iorporation, New York, N.Y., a corporation of alkyl amine. The use of a‘medium other than water ‘has the advan tage that: (a) The "composition ‘may be formed and'stored as an entity, since ionisation and condensation cannot take place sufliciently until the‘solv'ent evaporates as the ap‘ plied coating dries; -New York (b) Water-resistant and water-‘insoluble ?lm forming No Brewing. Fiied May 25, 1958, SenNo. 737,532, ingredients, which are ‘usually insoluble in water and Ciaims priority, application Great Britain May 27, 1957 10 therefore increase the moisture resistance of ‘the ?nished 7 tllaims. (Cl. 26tl—2.5) coating, may be incorporated in‘ solution: and (c) The Water-soluble ingredients will‘not now crystal It is 'generally'acknowledged thatthe mostsuccessful lise as the-solvent of the medium evaporates, and since way of imparting ?re retardance to'a combustible mate rial such as ‘wood or'materials made therefrom (e.g. 15 a mixture of relatively long liquid life is produced, ?llers or pigments may be intimately dispersed 'in'the medium cardboard, hard or ‘soft ?bre insulation board and the by mechanical milling and the cornbined‘rcsult is that a like) isby ‘applying a surface coating which is poten coating of enamel-like ‘appearance can be produced. tially intumescent. Such a coating swells‘ under heat or It is generally preferred that the non-aqueous in direct ?ame to produce .a puffed-up, non-glowing insulat ing cellular mat which insulates the substrate material 20 tumes'cent‘?re retardant composition according to the in vention shall comprise not only urea but also a phenol, from the heat source and at the same time excludes oxygen. The principle is also advantageous in delaying heat transfer to a treated metal surface. each partiallycon‘densed' wlt'h'fo'rmaldehydein an' organic solvent medium. ‘A ‘particularly suitable‘organic solvent is one that‘is 'or ‘comprises ‘a lower-‘aliphatic alcohol, Typical among such products is'a composition which incorporates a foaming ingredient (e.g. mono- or di 25 such as'm'ethanol'or‘ethanol. ‘Such'alcohol'may be used together with‘anaromatic‘ hydrocarbon such as xylene. ammonium phosphate), urea and formaldehyde in a state ‘If the ‘compositionis required ~to‘ give ‘a surface ‘coat of condensation and an amylaceous substance such as ingot an opaque'or enamelslike‘character there is incor starch. These ingredients in a ?nely pulverized state ‘are porated therein a substantial amount of a water-insoluble mixed in optimum proportions, together with inert pig ments which impart colour and/ or opacity to the coating, 30 ?ller or pigment which may be for example rutile, ana tase, asbestine, mica, vermiculite and/ or antimony oxide. and applied to the potentially combustible surface as an aqueous slurry or suspension. Suclia composition is described in British patent speci?cation No. 632,844. There are two main disadvantages with the above com In this case it is particularly desirable that‘ thecomposi positions. Firstly, the curing of the coating is brought 35 about by the chemical condensation of urea and form In the case that the composition is required to produce a transparent surface coating, the foaming ingredient tion should include phenol as wellas ureacondensed with formaldehyde. aldehyde, catalysed by mono-ammoniurn'phosphate or should be a salt or salts, with ammonia or an amine, other acid source; these three ingredients (which com bination produces with heat one of the best foam mats of an organic partial ester of orthophosphoric acid, before the composition is to be applied as a coating. otherwise the whole solidi?es in the container. The dis when the organic solvent ‘medium evaporates from an because ammonium phosphates such as mono- or di known) cannot, therefore, be mixed for many hours 40 ammonium phosphates are liable to‘ become opaque applied coating. In some cases, instead ofincorporating a straight urea composition as two components which have to be in" 45 formaldchyde condensation product in the composition, there may be employed an~alkylated,e.g. butylated,'urea timately mixed before use, and this 'is frequently in advantage is overcome in practice by packaging the formaldehyde resin. This may be particularly useful convenient. Secondly, the most effective foaming ingre when preparing compositions for producing ‘transparent dients are highly water-soluble, and coatings produced surface coatings, and his then desirable that the foaming from compositions containing these ingredients are water ingredient shouldbe an organophosphoric acid ester as sensitive and subject to e?lorescence throughout their 50 hereinbefore mentioned. life. Moreover, since they are water-soluble, the slurry A plasticizer is usefully incorporated in the composi referred to is in fact a saturated solution, and as the water evaporates from the applied coating, undesirable crystals are grown, providing a ?nished surface of rough texture. The main obg'ect of the present invention is to produce intumescent compositions which will overcome the afore tion, particularly in the case of a composition for pro ducing transparent surface coatings, and‘particularly'use ful plasticizers are ‘glyceryl-a-tolyl ether and glyceryl'di tolyl ether. As hereinbefore indicated, the compositions of the invention may incorporate, as a‘further addition, a Water said disadvantages and which will be adapted to produce resist-ant and water-insoluble ?lm-forming resin. The following indicates howtypical-compositions ac~ 60 cording-to the invention may be produced: have an enamel-like appearance. Urea and formaldehyde (or asubstance'such as hexa An intumescent composition according to theinvention methylene tetramine which liberatesformaldehyde), to is essentially non-aqueous and comprises urea and form gether with a phenol ‘or a substituted-phenol; are. mixed aldehyde partially condensed in a volatile organic solvent together and s-tirred‘into an appropriateprioportion (in medium, and a foaming ingredient which may be an surface coatings which may be transparent or which may ammonium phosphate, cg. a mono- and/or di-ammoni um phosphate, or a salt or salts, with ammonia or an amine (preferably a lower alkyl amine), of an organo partial ester of orthophosphoric acid. A particular example of a foaming ingredient of the latter type is a mixture of mono-butyl and di-butyl phosphates together with a minor amount of free orthophosphoric acid com dioated .by examples hereinafter) »of 1 a non-aqueous solvent, more particularly a lower ‘aliphaticalcolrol. A certain degreeof condensation is. then allowed orcaused to take place bylreeping the mixture for latime at a '.pre— 1 determined temperature, ‘or during ; a .sequence ;:of time/temperature conditions. This will be-made' ,clear ' by stating that if methanol is used as a‘solvent asuitable vheating sequence is a period of gentle refluxing at 65 .to 3,077,458 3 4 70° C. for about 11/: hours, whereafter the ethanol or substituted phenol is added, and which is then followed by refluxing for a period of between 1A2 to 4 hours. It is not possible to assess the precise degree of resin con densation which results from this procedure but it may be said that the optimum is when the condensation prod ganic solvent medium evaporates from an applied coating. However, by replacement of the monoammonium phos phate by a mono- or d-i-substi-tuted organo partial ester of orthophosphoric acid, a coating which dries and re mains transparent is obtained. Example VII uct has a viscosity, at room temperature, in the range of 20-30 seconds No. 4 Ford cup. The pnoduct, which constitutes the resin ‘or binder constituent of the com The resin or binder is prepared in the manner desmibed hereinbefore, and mixed with the other ingredients to position, is then cooled and thereafter the ?nely pulverised 10 form a composition typi?ed by: foaming ingredient and ?ller or pigment (if required) are stirred in. Parts by weight The mixture may then be raised again to a temperature of, say, 60° C. for a 1/2 hour to eifect Urea ____________________________________ __ 11.4 further condensation. Final mixing and dispersion may Parafornraldehyde 15.9 be effected by mechanical means such as are typically 15 Phenol __________________________________ _.. used in the paint industry. The following ‘are examples of formulations for the Ethanol production of non-aqueous intumescent ?re retardant compositions according to the invention in accordance with the procedure indicated generally above. ________________________ __ 36.1 Monobutyl phosphoric ‘acid ________________ __ Dibutyl phosphoric acid ___________________ __ 12.5 5.3 Ammonia (anhydrous) ____________________ __ 20 I Example 1 Piara-chloro-meta-xylenol 15 .0 Glyceryl a-tolyl ether _____________________ __ 7.5 100.0 weight 25 Glyceryl a-tolyl ether acts as a plasticizer in the above composition, and serves toincrease resistance to crazing (“cold-checking”). As an alternative to glyceryl a-tolyl ether, this material may be replaced by an equal weight Formaldehyde _____________________________ .._ 15.9 Phenol ___________________________________ __ 4.1 Methanol _________________________________ __ 28.1 of glyceryl di-tolyl ether. Para-chloro-meta-xylenol also Mono-ammonium phosphate _________________ -1 27.0 Anatase __________________________________ __ 2.7 Asbestine _________________________________ __ 10.8 2.2 __________________ _ _ Percent by Urea _______________________________________ -i 11.4 4.1 _________________________________ __ 30 serves to increase resistance to crazing, but more par ticularly to increase moisture resistance. As an alternative to the use of the particular resins 100.0 prepared as described hereinbefore, the materials which impart ?re retard-ance and those which plasticize the resin may be mixed advantageously with a bu'tylated urea fornraldehyde resin syrup of ‘the type commercially avail able. The proportion of resin syrup to other materials Example 11 As Example I but with resorcinol or para-chloro-meta xylenol instead of phenol. Example Ill (excluding solvents) necessary to produce a coating with good drying properties consistent with an adequate stor— As Examples I or IE but with some or all of the anatase replaced by antimony oxide. Not only is the antimony 40 age life has been found to be much higher than in Ex ample VII, ‘and a typical composition is as follows: oxide merely an alternative “?ller” to the \anatase, but under ?re conditions it is reactive with chlorine-contain Example VIII ing compounds if such are present in the composition and Parts by forms antimonyl chloride, which is Well known as a weight ?ame-extinguishing gas. Butylated urea formaldehyde syrup, 55% solids Example IV in butanol/xylol _______________________ __ Monobutyl phosphoric acid _______________ .._ As any of the above examples but with some of the Dibutyl phosphoric acid __________________ __ inert ?ller replaced by a material such as mica or vermicu lite which will exfoliate under ?re conditions to give added 50 Monomethylamine _______________________ __ Ethanol ________________________________ __ ?lm thickness. These materials are also more refractory Para-chloro-meta-xylenol __________________ _._ than the carbonaceous/phosphate foam mat, and hence Glyceryl a-tolyl ether _____________________ __ give increased resistance to ?re. Example V As any of the above examples but with a silicone (e.g. an organo polysiloxane) incorporated to increase water repellency. ' Example Vl 75 7.25 3.10 1.50 5.65 5.00 2.50 100.00 55 Additional resistance to “cold-checking” may be imparted by the addition of up to 10% of tris ?-chloroethyl phos phate, weight by weight, to the mixture of Example VIII. What We claim is: As any of the above examples but with a water-resist 60 1. A substantially non-aqueous intumescent ?re ant resin or other compound incorporated (e.g. a cyclic retardant composition comprising a condensation prod ketonic resin or urea formaldehyde-toluene sulphonamide uct and a foaming ingredient in admixture in a 1 to 2 complex). Additions of the order of up to 10% of these carbon atom alkanol as solvent, said condensation prod ingredients on the composition given in Example I im uct being a 1 to 2 carbon alkanol soluble urea-formalde part useful properties, especially with reference to re hyde condensation product and said foaming ingredient sistance to moisture. being selected from the group consisting of ammonium There are many occasions when a transparent rather and lower alkyl-arnine salts of from mono to dibutyl esters than an opaque lacquer is required; e.g. when a wooden of o-phosphoric acid. or veneered surface is to be ?ame-proofed but at the same 2. A composition according to claim 1 in which the time it is desired to retain the attractive appearance of 70 foaming ingredient is formed by reacting ammonia with the natural grain. Such a lacquer cannot be obtained merely by the elimination of the opaque pigments (e.g. anatase, asbestine, mica) from the compositions given in Examples I to V1; the foaming ingredient (e.g. ain monobutyl phosphoric acid. 3. A composition according to claim 2 in which the foaming ingredient is formed by reacting monomethyl monium phosphate) also becomes opaque when the or 75 amine with dibutyl phosphoric acid. 8,077,458 5 6 4. A composition according to claim 1 in which the composition is produced from the following com ponents: Parts by weight Urea Parts by weight ____________________________________ __ Paraformaldehyde 5 Butylated urea formaldehyde syrup, 55% solids Phenol __ Ethanol ___ 11.4 _________________________ .._ 15.9 ____ __ 4.1 .. 36.1 75 Monobutyl phosphoric acid __________________ __ 5.3 Monobutyl phosphoric acid _________________ __ 7.25 Dibutyl phosphoric acid _____________________ __ 3.10 Ammonia (anhydrous) _____________________ __ 2.2 in butanol/xylol _________________________ __ Monomethylamine _________________________ __ 1.50 Ethanol Para-chloro-meta-xylenol ____________________ __ 15.0 p 10 Glyceryl a-toly-l ether _______________________ __ __________________________________ __ 5.65 Para-chloro-meta-xylenol ____________________ __ 5.00 Glyceryl a-tolyl ether ______________________ __ 2.50 5. A composition according to claim 1 in which the 15 resin is a urea, phenol and formaldehyde condensation product having a viscosity, at room temperature, in the range of 20-30 seconds No. 4 Ford cup. References Cited in the ?le of this patent UNITED STATES PATENTS 2,650,206 Stock _______________ __ Aug. 25, 1953 2,676,162 Marotta _____________ __ Apr. 20, 1954 785,977 Great Britain __________ __ Nov. 6, 1957 FOREIGN PATENTS 6. A composition according to claim 5 in which the 20 phenol is para-chloro-meta-xylenol. 7. A composition according to claim 5 in which the composition is produced from the following components: 7.5 OTHER REFERENCES Ellis: “Chemistry of Synthetic Resins,” volume 1, pages 672-678, copyright 1935, Reinhold Pub. Corp, New York.