Document 3Q6q77XykvgVbXJy0dvbpVb90

FILE NAME: Phenolic Resins (PHR) DATE: 1962 Jan 23 DOC#: PHR047 DOCUMENT DESCRIPTION: Patent - Composite Sheet; from Westinghouse File PLAINTIFF'S EXHIBIT < Q tc w u J ^ Jan. 23, 1962 w . c. h o o d e t a i 3,018,206 FIRS-RESISTA!.'" DECORATED COMPOSITE LAMINATE MEMBERS ' ANO METHOD OF PRODUCING SAME Filed Oec. 31. 1957 C Overlay Sheet Impregnated with n/' ( A WITNESSES INVENTORS W illiam C Hood 8 ^^pavid E Baldwin ATTORNEY p r o p r i ( i . EXHIBIT I United States Patent Office Patented Jan3.,0231,8,1290662 1 2 j.m iunr. prcpnnted protective overlay sheet is employed O'er f i r e -r f .s is t a n t d f c o k a i f .d c o m p o s it e i .a m - sheets having designs imprinted thereon to provide better JNATE MEMUFIJS A M ) M ETHOD OF IMtODDC- abrasion resistance and good surface appearance theic- INC SAMF. to. Pigmented sheets that have no design imprinted William C. Ilnnd. Vnrnvillr. ami I1;i*i<! E. Baldwin, o thereon will ordinarily have good abrasion resistance H am pton. S.C., atvi|>tion In \V n'iii;liirac K lcdric and hence an overlay sheet is not required. Suitable ma Corporation. East PidUmi gli. Fa., a corporation of terials for overlay sheets include rayon, glass fabric and Pennsylvania ,, Filed Occ. 31. 1957, 5r. No. 706.31* alpha-ccllulosc paper. In accordance with this invention, when an overlay sheet is employed, it will be impreg 5 Claims. (Cl. 154-- 45.9) 10 nated with a clear melamine-aldehyde resin. This invention relates to composite laminate members Any commercially available asbestos paper sheeting and particularly to composite decorated laminate mem uch. for example, as that available under the proprietary bers having good fire-rcsistancc ar.i to the method of name Novahestos, may be employed in preparing the producing same. laminates of this invention. Decorated laminate members have enjoyed wide If. Sheets of asbestos paper are impregnated with any spread use in the building industry, especially as deco well known conventional thermosetting phenolic resin rative wall panels, ceiling panels and the like. Many prepared hy reacting phenol, cresol. or crcsylic acid with applications require that the decorative panels be fire- formaldehyde, paraformaldehyde or other polymers of resistant. This is particularly true when the decorative formaldehyde, ordinarily in the presence of an alkaline panels are used as bulkhead construction in ships, and 20 catalyst such as ammonia, sodium hydroxide. lime, or wall construction in hospitals. olTicc buildings and the barium hydroxide. A volatile solvent such as ethyl al like. Heretofore, attempts have been made to produce cohol. toluene or xylene is added to the resin to produce fire-resistant decorated laminate members, however, the an impregnating varnish. The resin solids content of laminates have not possessed adequate physical strength the varnish may be varied from about 20% to 60% by and other desirable physical properties. Attempts to zr, weight. improve physical properties have resulted in a consid A suitable resin may be prepared by reacting 1 mol erable reduction in firc-rcsistancc to a point where the of phenol and from 0.9 to 1.7 mots of formaldehyde in material could not be classified as fire-resistant. It is a closed reaction vessel under reflux conditions for at highly desirable to have available in the art decorated least 1 hour, the reaction being catalyzed by an alkaline laminate members that have good fire-resistance and high 30 catalyst such as ammonia and then vacuum dehydrated physical strength. at a temperature not exceeding 100* C. The object of this invention is to provide composite Example I decorated laminates comprising sheet fibrous material The following is an example of the preparation of a impregnated and bonded together by thermoset resinous compositions, which laminates have good fire-resistance 33 partially reacted thermosettable phenolic resin that may be employed in carrying out this invention: and high physical strength. Into a steam heated reaction kettle there are intro Another object of this invention is to provide a method for producing decorated laminates of high physical duced the following: Parts by weight streOntghtehr aonbdjegcotsodoffitrhci-srcisnivsteannteioe.n will, in part, be obvious 40 PFhoermnoalld_e_h_y_d_e_ .(.3.7.%. .) . ___________________. _. ._._._._._._._._________110104 and will, in part, appear hereinafter. Ammonia (28% ) ___________________________ 3.73 For a better understanding of the nature and objects of the invention, reference should be had to the follow These materials are reacted in the steam heated reaction vessel at a temperature of approximately 100* C. under ing detailed description and drawing in which the single 45 reflux conditions for a period of about lVi hours. The FIGURE is a schematic view of an assembly of sheets in mixture is then dehydrated under a vacuum of 28 inches accordance with this invention. of mercury, and the temperature gradually increxsed to In accordance with this invention a decorated com approximately 75* G during dehydration. Substantially posite laminate member is prepared which has good fire- ail the water is removed. To the hot reaction product resistance and high physical strength. The composite 60 there is added 81.5 parts by weight of 95% ethyl alco Laminate member comprises a core or body layer com hol and the resulting resin varnish is then permitted prising a plurality of sheets of asbestos paper impreg to cool to room temperature. This resin vamish has a nated with a phenolic condensation product and a deco viscosity of from 180 to 400 ccntipoiscs at 25* G and a rated surface layer impregnated with a clear mclaminc- set time of from 13 to 16.5 minutes at 153.5* G aldebyde resin. 6S Another particularly good resin composition that may The decorated laminate members of this invention he employed in impregnating the sheets of asbestos paper will usually be adhesively bonded to a rigid backing sheet is a dicynndiamide-phenol-formaldehyde resin composi of fire-resistant material having a thickness of from about tion. Such a resinous composition is derived by reacting Vi inch to 1 inch to provide suitable fire-resistant panels. phenol, dicyandiamide and formaldehyde in the propor The panels thus produced arc well suited for structural 00 tions of I mol of the phenol, from 0.8 to 2 mols of di materials for the marine industry, hospitals and the like cyandiamide and from 0.9 lo 1.5 mols of formaldehyde where fireproof structures arc required. An example of per mol of the combined phenol and dicyandiamide. a suitable rigid backing material N that available com Water is present, being.usually furnished as a part of mercially under the proprietary name Marinite. TTie aqueous formaldehyde solution (37% to 40% ), and adhesive eomposiiion employed is preferably a fire-re 0.1 amounting to at least 10% of the weight of the reactants, sistant type such as the silicon type adhesives. and ordinarily should not exceed the weight of the re The decorated surface layer may comprise a sheet of actants. The mixture is reacted under alkaline conditions alpha-ccllulosc raper, thin cotton fabric, silk, glass fab for at least Vi hour, and preferably by refluxing from 1 ric. asbestos paper or like fibrous sheet material with a to 2 hours, and then is vacuum dehydrated at a tempera design imprinted thereon or the slicct may be pigmented 70 ture not exceeding 100* C. until substantially all of the throughout. Pigmenied sheets with designs imprinted water is removed and then a volatile solvent is applied to thereon may also be employed. Ordinarily, a resin im- produce an impregnating varnish. 3, 010,200 , _ . .. , .he n?bestos The resin varnish employed to impregnate ^ e osbest^ . 4 one or more times until it has picked up resin solids in in of from 0.3J to 0.80 times the weight of the dry paper sheets may include a sm. I p P . .J . :nor_3n;c asbestos paper and the varnish impregnated asbestos of 2% to 10% by weight, o ine y I oxide and 'paper is passed through an oven or other dryer after each sohOs such- silica, aluminum "" T 0" . * 5 L P rcm0vc the volatile solvent. During drying, it is the like refractory solids to impar . desirable to heat the asbestos paper treated with the to the final product. _ . - r the method of varnish composition at a temperature of from HO* C. to dehyde resin for use m this inventson. ^ J 3se> Thc heat treatment of the applied resin at this Example II , I;ipC j conducted so that thc resulting treated fabric bis Into a steam heated reaction kettle there are introduced followlne- a "greenness" of from 0.3% to 6%. Tji* cr.es" e" '* determined by placing a stack of small pieces of the resin *' p artj by weight treated sheet material in a hot press and Pres*mf 11 at * pvrf,ni ............................ ................ 2750 15 temperature of 175* C. and a pressure of 1000 pounds n>vmiHmide 2100 per square inch for 5 minutes, and then measuring the Pormaldehvde (37% ) 4620 amount of resin that is forced out of the stack, that is. Ammonia i?8 % ) ................................ I _______ 16 Ammonia (2 8 , ) ------------------------------ -------- Hi* resin that extends beyond the fibrous sheet material and delcrjnininB the prop0rtion of tins exuded The ammonia and the formaldehyde arc admixed betore 2(J rcjin lQ ,he t01a| weight of thc sample, being introduced into the kettle with thc remainder ot jt a]w cs, ent;aj (hat thc greenness be controlled and the ingredients, the mixture having a pH of approximate- ( wj|,)in ,hc ab0vc limits. It is important to have ade- ly 8.5. The mixture is slowly heated, and at 80 C. an ,e Srcenncss s0 that a homogeneous laminate is ob- exothermic reaction takes place that carries the tempera- ,aincd However, if thc greenness is too high, a burst- turc to approximately 95* C. Additional heat is then ^ ^ ,|tc anhc<|PS fibers is encountered during laminat- supplied in order to cause the reaction mixture to reflux. j|ls procew 3n(| the resin tends to How into the decorated The mixture is refluxed for 90 minutes and then deny- j ' r caiising a discoloration of same. Details of the drated under a vacuum of 27 inches of mercury, and tne |aminating procedure will be set forth hereinafter, temperature gradually increased to approximately 75 v. j j )C decorated sheet material and protective overlay, if during dehydration. Substantially all the water '* re* 39 one s employed, are impregnated with at least 50% of moved. To the hot reaction product there are aoaca their we;-|U with 3 clear thermosetting melamine-aldehyde 2000 parts by weight of 95% etbanol, and the resulting resjn. It will be appreciated that in many cases, toe thick varnish is cooled to room temperature. The resin- melamine-formaldehyde resin have been made in the pres et reaction product is then further diluted w ith a mix- ence o{ butano, and lhal they comprise butylated poly- - ture comprising 50% by weight of ethanol and 50% by M merJ^ Thc tcrmJ "melamine-aldehyde" are intended to weight of water to produce an impregnating varnish com- _jy t0 lucj, compositions which comprise essentially prisinc approximately 53% by weight of resin s01'*" - theJC reactants as the main ingredients but may contain The viscosity of the composition is approximately zau olber ingredients such as sulfonamides, glycols, glueosides ccntipoiscs at 25* C. . .. . Particularly good results have been obtained by im- and the like which are added to provide special properties jueh M flexibility, craze-resistanee and the like. Tne pregnating sheets of asbestos paper with a mixture of manufacture of the melamine-aldehyde resins suitable for from 2 parts to 4 parts by weight of a conventional the practice of ,he prcsent invention is well known m the- phenolic resin and 1 part by weight of a dicyandiarmae- ^ amJ nced not be dctaj|cd herein. . phenol-formaldehyde resin dissolved in a suitable solvent Referring to the single figure of the drawing there ts such as ethyl alcohol to provide a varnish composition sh0wn a stack 10 which comprises sheets 12 of absestos having from 20% to 60% resin solids. > impregnated with B-stage phenolic resin, decorated The following example is illustrative of a suitable mix- jheet I4 and protective overlay sheet 16 both of which ture to be employed in carrying out this invention. are impregnated with B-stage melamine-aldehyde resin. Example III Three parts by weight of the resinous reaction Product of Example I and one part by weight o t the| jetunous reaction product of Example 11 and 5 parts by we,ght of 95% ethyl alcohol are thoroughly admixed by agiti tion to form an impregnating res.nous varn.sh composi tion. This resin varnish has a viscosity of from 60 o 150 centipoises at 25* C. and a set time of from 13.5 to The stock 10, as shown in the figure of the drawing u *n introduced into a molding press where the stack is sub- 60 ^ fo|> a dfied pcn-od oi time to a temperature of j fQm abQut 26Q. p t0 320. F ., while under pressure, prcsjurcj of from J00 p.sj . ,0 1500 p.s.i. are sausfactory. wh|.,e ures of from j 000 p.s.i. to 1200 p.s.i. give best , curinB cycIc must be closely controlled so C5 complete cure of the melam.ne-ildehyde |he phcno|ic resin will be effected. Adequate 17.5 minutes at 153.5* C. . ,,..u The sheets of asbestos paper may be impregn curing of the resin components is obtained in about 15 minutes to 25 minutes at a temperature of from about the resin varnish composition of this j aa 260* F. to 300* F. . , ventional manner, for example, as>**5,be1<j ; mo(?r!anL The following examples illustrate the preparation of to Wellman et a l. Patent No. 2,579.637. It is P composite decorated laminate members in accordance foofrththee ipmuprpreogsensanotf w.thm the r"e"lati"ve' ^ly^ n^aV^oVw irnansgeeo f with this invention. Exampl,e IwV the'weichl of Vhe nUet"d*fabrS plus the weight of the 5 Eight sheets of asbestos paper (12 inches x 12 iaebat x r ^ n that is impregnated in the sheet to the weight of the 0 0 l0 inch, are mpiesTM" * w.th th. ph.nohe m m - untreated fabric. In other words, the treated fibrous ma- nilh o( S a m p le I. to a resin ratio of about 1.60 and terial carries resin in aa amount equal to from 35 -o to sfCennesJ 0f about 1.0% and the solvent remo 80% of the fibrous material alone. T o achieve the ulti- jheel (J2 nches x , 2 inches x 0.010 inch) of P'P"en mate in fire-resistance the very minimum amount o fje sia 70 a,pha.cel|u!ose paper is impregnated with me'a^ "f 'a`<TQ is desired; however, to obtain desired physical PrPer,`* such as good moisture resistance, g ^ d dimensional sta hyde rM|n varnish to provide a resin ratio of about 2.20 ^ jo,ent ren,0ved. A stack was prepared by surer- bility, good impact strength and the like. imposing one sheet of impregnated nshestos paper o greater amount of resin content is desired. varni, h . . other aod the impregnated pigmented sheet placed on th Thus, asbestos paper sheeting is dipped in tbe varmsn 70 oiu r 3, 018,208 top of the tacked asbestos sheets. The stack is consoli ing. (2) superimposing a plurality of layers of the resin dated or molded into a composite laminated member at a treated asbestos paper sheeting to provide a stack. (J) pressure of 1000 p.s.i. and at a temperature of about 280* superimposing a decorated sheet of fibrous material im F. for a period of about 19 minutes. The resulting lami pregnated with a potentially thermoscitable clear mela nate has good surface characteristics, good physical proper- 0 mine-aldehyde resin on top of the stack to provide a com ties and good fiic-rcsistance. posite member, and (4) molding the composite member at a pressure of from 500 to 1500 pounds per square inch Example V at temperature of from 135' C. to 165* C. Ten sheets of asbestos paper (12 inches * 12 inches x 2. The process of claim I wherein a protective over 0.010 inch) arc impregnated with the phenolic resin var- io lay sheet of fibrous material impregnated with a poten nish of Example II. to a resin ratio of about 1.60 and a greenness of about 1.0% and the solvent removed. One tially thcrmoseitahlc clear melamine-aldehyde resin is superimposed on top of the impregnated decorated sheet sheet (12 inches x 12 inches x 0.010 inch) of pigmented prior to molding. alpha-cellulose paper is impiegnatcd with melamine-alde 3. A fire-resistant decorated composite laminate mem hyde resin varnish to provide a resin ratio of about 2.00 16 her comprising (A) a surface layer comprising a decorate and the solvent removed. In accordance with the method sheet of fibrous material impregnated with a thermose of Example IV a composite decorated laminate member melamine-aldehyde resin and (B) a body layer eomprisin is prepared. This laminate has good surface quality, ex a plurality of sheets of*sbesios_pacr impregnated with cellent fire-resistance, and high physical strength. a* thcrmo'cl resin 'composition comprising from 35% to 80% of the weight of the asbestos paper alone, the thcrnio- Example VI ^ set resin composition consisting of (1) from 2 parts to 4 Six sheets of asbestos paper (12 inches x 12 inches x 0.010 inch) were impregnated with the phenolic resin varnish of Example III. to a resin ratio of about 1.60 on a greenness of 1% and the solvent removed. One sheet 23 (12 inches x 12 inches x 0.010 inch) of pigmented alpha cellulose paper having a design imprinted thereon and one sheet (12 inches x 12 inches x 0.010 inch) of rayon fabric are impregnated with melamine-aldehyde resin varnish and the solvent removed. The sheet of alpha- 30 cellulose paper is provided with a resin ratio of about 1.70 and the rayon sheet with a resin ratio of about 3.00. A stack is assembled by superimposing one sheet of impreg nated asbestos paper on the other. The sheet of pig mented alpha-cellulose paper is placed on top of the stack S3 and the rayon sheet is plated on lop of the pigmented sheet. In accordance with the method of Example TV a ^flmposite d e co ra te d laminate member is prepared. This decorated laminate member is adhesively bonded to a one inch thick sheet of Marinite bv using a heat resistant <0 adhesive composition to produce a composite member.. This composite member was tested using the Underwriters! Laboratories, Inc., test entitled `Tunnel lest lor Fire Re sistance of Building Materials." The foliowinc results*, were obtained: 48 parts by weight of a phenolic resin derived by reacting 1.0 mol of a phenol and from 0.9 mol to 1.7 mols of form aldehyde under reflux conditions for at least I hour, the reaction being catalyzed with an alkaline catalyst, and then vacuum dehydrated at a temperature not exceeding 100* C. and (2) one part by weight of the resinous reaction product derived by reacting one mol of a phenol, from 0.8 to 2.0 mols of dicyandiamide. and from 0.9 mol to 1.5 mols of formaldehyde per mol of the combined phenol and dicyandiamide in the presence of water, the mixture heing refluxed for at least Vi hour, and then vacuum de hydrated at a temperature not exceeding 100* C . the-said decorated sheet and asbestos sheets being consolidated and bonded together into a unitary member. 4. A thermosettable resinous composition consisting of ( I ) from 2 parts to 4 parts by weight of a phenolic resin derived by reacting 1.0 mol of a phenol and from 0.9 mol to 1.7 mols of formaldehyde under reflux conditions for at least one hour, the reaction being catalyzed with an al kaline catalyst, and then vacuum dehydrated at a tempera ture not exceeding 100* C . and (2) one part by weight of the resinous reaction product derived by reacting one mol of a phenol, from 0.8 mol lo 2.0 mols of dicyandiamide. and from 0.9 mol to 1.5 mols of formaldehyde per mol of the combined phenol and dicyandiamide in the presence Rate of flame sp re a d --------------------------- -- ---- --L L . of water, the mixture being refluxed for at least Vi hour, Fuel contributed - ___________ _________ ----------- and then vacuum dehydrated at a temperature not exceed. Smokc developed . --- ------------- ------ --------- --- ---_ JL - It will be understood that the above examples and de- 60 scription and drawing are illustrative and not in limitation of the invention. We claim as our invention: 1. In the process of preparing a fire-resistant deeorated composite laminate member, the steps comprising (1) 35 impregnating asbestos .gaper sheeting with a solution of a CEermoseiiaBIe.ixesioous composition consisting of (A) from 2 parts to 4 parts by weight of a phenolic resin de rived by reacting 1.0 mol of a phenol and from 0.9 mol to 1.7 mots of formaldehyde under reflux conditions for 00 at least one hour, the reaction being catalyzed with an al kaline catalyst, and then vacuum dehydrated at a tempera, ture not exceeding 100* C. and (B) one part by weight of ing 100* C. . . . . 5. A resinous impregnating varnish composition con sisting of (1) from 2 parts to 4 parts by weight of a phenolic resin derived by reacting one mol of a phenol and from 0.9 mol IO 1.7 mols of formaldehyde under re flux conditions for at least 1 hour, the reaction being catalyzed with an alkaline catalyst and then^vacuum de hydrated at a temperature not exceeding 100* C (2) one part by weight of a resinous reaction product derived by reacting 1 mol of a phenol, from 0.8 to 2.0 mols of di cyandiamide. and from 0.9 mol to 1.5 mols of formalde hyde per mol of the combined phenol and dicyandiamide in the presence of water, the mixture being refluxed for at least Vi hour, and then vacuum dehydrated at a tem perature not exceeding.100* C . and (3) a solvent therefor. the resinous reaction product derived by reacting one mol of a phenol, from 0.8 mol to 2.0 mots of dicyandiamide. 03 and from 0.9 mol to 1.5 mols of formaldehyde per mol of References Cited in the file of this pateot UNITED STATES PATENTS the combined phenol and dicyandiamide in the presence of water, the mixture being refluxed for xt least Vi hour, and then vacuum dehydrated at a temperature not exceed ing 100* C.. the resin impregnated sheet fibrous material 70 being heated to drive olT the solvent and to advance the cure of the resin to a condition where its greenness is from 0.3% to 6% . the asbestos paper sheeting carrying from 0.35 to 0.80 times its weight of the resin after dry 2.439.929 2.604.427 2.732.325 2.740.737 2.801.198 2.801.672 2.824,849 Hill et .................................. ** Armstrong et a l . ..................., " ,y Lindenfelscret a l ...................J - 24- 19f Elmer et a l . ------------------- . , j 957 M om s et al............................ J"ly 3 T Baldwin et al....................... - A Boiney................................... Feb' 2S' 1958