Source: https://patents.google.com/patent/US1905999A/en
Timestamp: 2018-09-19 19:33:49
Document Index: 502362950

Matched Legal Cases: ['in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine', 'in fine']

US1905999A - Catalyzed urea resin - Google Patents
Catalyzed urea resin Download PDF
US1905999A
US1905999A US42743530A US1905999A US 1905999 A US1905999 A US 1905999A US 42743530 A US42743530 A US 42743530A US 1905999 A US1905999 A US 1905999A
Ellis-Foster Co
1933-04-25
Patented Apr. 25, 1933 UNITED STATES PATENT OFFICE CARLETON ELLIS, F ZKONTCLAIR, NEW ZI'EI5SEY,- ASSIGNOR TO ELLIS-FOSTER COMPANY,
I A CORPORATION OF NEW JERSEY CATALYZED UREA RESIN No Drawing.
This invention relates to resinous products derived by aldehydic condensation of urea and/or thiour'e'a and/or other resinifying urea derivatives and the cellulose complex thereof.
.The object of the invention is to provide a complex adapted for use in the plastic arts.
The complex may be considered from two standpoints: (l) as a primary complex; and (2) as a secondary complex.
The primary complex is constituted by either (a) urea aldehyde condensation products, particularly such products derived with the aid of formaldehyde; or (6) such products incorporated with a modifying agent of resinification, such as the condensation prod nets of thiourea and an aldehyde, specifically formaldehyde, or a resinous material of the type of an acetone resin made by reacting on acetone with an aldehyde such as formaldehyde or various other resinous modifying agents, as will subsequently bemore fully described.
Reference is made to companion copending applications for subject matter utilized in earrying'out the present invention and described at least in part in those. several applications. In application, Serial No. 689,- 165, filedJanuary 28, 1924, entitled White synthetic resin and process of making same, there is described resins of the urea type such as the condensation products of urea and formaldehyde, and methods of making such resins, the claims being directed to the urea resins produced by the utilization of acids, particularly inorganic and organic acids, and the further treatment of such condensation products by heat and heat and pressure to affect the characteristics of these condensation products, including also the reaction with the resins ofagents which affect the characteristics of the co densation products, such as tempering agents, including casein, etc. As noted, the claims of that companion application are directed to the resins and methods of making such resins referred to In the instant application, the claims are directed to molding compositions of par tieular characteristics in which the urea resins of that companion application, as well as Application filed February 10, 1930. Serial No, 427,435.
other types of urea resins, may be employed.
In companion application, Serial No. 694,- 420, filed February 21, 1924, entitled White plastic resin and process of making same, there is disclosed and claimed molding compositions and molded articles, as well as methods of producing such compositions and articles produced with urea resins, such as urea-formaldehyde resins incorporated with fillers and pigments, and particularly moldmg compositions containing'urea-firmaldehyde resins that are variously colored to produce multi-eoloredmolded articles, etc. The instant application is concerned with a more speelfic development of this character of molding compositions.
In companion application, Serial No. 735,- 600, filed September 3, 1924, entitled Urea product and process of making same, there is disclosed and claimed laminated products carrying sheet materials cemented or bound together with urea resins, and methods of making such laminated products, and also claims to the resins and methods of making the resins produced by simultaneous reaction 7 of aldehydes with both urea and thiourea, or related complex products. In the-instant application, the particular resins set forth in that companion case-may be employed along with other resins for producing the particular types of molding compositions claimed in the instant application.
In companion application, Serial No. 742,-
' 719, filed October 9, 1924, entitled Laminated pressboard and multi-colored articles and process of making same, there is disclosed and claimed laminated products or multicolored articles made from variously colored fragments of urea resins, as well as sheet materials such as paper carrying the urea resins. In the instant application, the claims are directed to particular types of molding compositions, in which the resins "and other compositions of the companion case may be employed.
In companion application, Serial No. 3,596, filed January 20, 1925, entitled Synthetie product and process of making same, there is disclosed and claimed methods of producing urea resins and the products resulting from such methods produced by the use of phenols or phenolic derivatives reacted with the urea resins.
In companion application, Serial No. 28,- 505, filed May 6, 1925, entitled Synthetic resin and process of making same, which is a division of companion application 689,165, referred to above, there is described and claimed the resins and methods of producing same in which the urea resins are produced by first reacting the ingredients such as urea and formaldehyde in an alkaline medium, followed by acidification, as well as methods for producing such condensation products when the reacting ingredients are processed together under more than atmospheric pressure, and in the presence of ingredients that modify the character of the condensations obtained.
As more particularly set forth below, subject matter is derived from these several companion applications, but the claims referred to above in those applications a re directed to particular types of compositions and methods of producing compositions that are different from the specific types of molding compositions claimed in the instant application for reasons discussed above, and apparent from the claims present in the record of this case.
In one modification of the present invention urea condensation products in conjunction with sulphur-containing resins are used together to form the basis of a plastic or resinous complex. In Serial 735,600 I have discussed the employment of mixtures of urea and thiourea reacted with formalde: hyde to form a plastic complex.' In the last mentioned application I have also indicated that the reaction between these urea materials and the aldehyde can be carried out in acid, alkaline or neutral solution. The present invention is in part concerned with production of an initial reaction product under conditions which are substantially neutral.
[React/n within the confines of neufra//'f z .-Reaction within the neutral zone, that is in that borderline between acidity and alkalinity. has in years past been determined by various indicators such as litmus. In my earlier applications where reference has been made to the conduct of the initial reaction under conditions of neutrality, I have made such determinations of neutrality by means of litmus. and the like. In recent years the hydrogen ion concentration method of determining acidity, alkalinity and neutrality has come into use with the provision of delicately adjusted indicators to make possible more accurate determinations than heretofore available with the aid of litmus and the like. According to authorities, litmus indicates neutrality between a pH of 4 or 5 on the one hand (acid side) and a pH of 8 on the other hand (alkaline side). Within these limits there exists what may be termed a neutral zone defining neutrality as originally expressed in terms of litmus or similar indicators. In the present invention I prefer to conduct the initial reaction between formaldehyde and urea and/or thiourea, etc., within the limits of such neutral zone. If the formalin solution employed is not adequately neutral it may be suitably neutralized to bring it within this neutral zone.
Period of /zcating.Reaction between the urea materials and the formalin may be carried out at elevated temperatures but below the boiling point of the liquid, as indicated in several of my earlier applications. Or a definite temperature of reaction, namely, the boiling point may be taken and the time of heating reckoned on that temperature. IVithin the neutral zone the reaction takes place with a sufficient degree of rapidity at, the boiling point (which is usually a degree or two below 100 C.) permitting a syrupy product to be prepared by conducting the reaction for periods ranging from minutes to 2 or 3 hours. Considered from the standpoint of pH. the time of reaction may be stated in a very rough way to vary inversely as the hydrogen ion concentration increases. During the heating there is usually a very slight increase in pH value. A reaction mixture which in the cold showed a pH of 6, after minutes boiling showed a pH of 5.2 after 1 hour pH 5.2 and after 1% hours pll 5.1. At this stage the reaction mixture gelled. In another observation a batch having an initial pH of 5.6 showed pH 5.1 at the end of half an hour. The change in pH by heating, therefore, is very slight and apparently does not at any time carry the reaction mixture out of the neutral Zone when the reaction has been initiated under said neutral conditions. Therefore operating under these conditions I may start with an initial pH ranging from 7 or 8 down to 4 without sacrificing that condition of neu trality expressed, for example, in Serial No. 735,600. Preferably the reaction is carried out at atmospheric pressure employing a reflux condenser which substantially prevents the admis ion of air during the reaction. In other cases reaction may be carried out in autoclaves at pressures above atmospheric.
Relation of lzcatiny to drying.The time of heating is in some manner connected with the release of moisture from the resinified material (hiring the drying period. Certain conditions are. imposed with respect to drying temperatures in order to prevent conversion of the material during drying to a stage where it will not fiow properly in the mold. It is of great importance to avoid this pro-curing condition because for molding purposes a con'iposition must be prepared which will soften and flow freely to perhaps slightly higher, to avoid pre-curing all parts of the mold forming sharp edges or otherwise taking a clean-cut impression of the mold and thereupon to set promptly,.that is cure, yielding a hard thermo-set shaped article. As will be subsequently more fully discussed, a material ofithecellulose type preferably is incorporated with the resin, especially while the latter is in its intermediate syrupy stages. Thereupon the material is dried. This may be conducted, as I have specified in certain of my patent applications, in a vacuum dryer. A procedure which allows the employment of cheaper equipment is drying in the open as, for example, air drying followed by exposure to a gentle heat. A simple manner of drying is to expose the composition on screens made from nickel or Monel metal wire placed in a drying room throughwhich a circulation of air is maintained to heat the'material to a temperature of, say, 40 to 50 C. It is possible to advance the temperature to or C. or even higher in some cases, provided the time of heating is not protracted to cause objectionable precuring. While the composition is still quite moist the. higherrtemperatures may be employed rather freely without danger of precuring. But as soon as the bulk of the mois ture has departed then there arises this danger. It is better, therefore, to dry at lower temperatures, for example, around 50 6.; or
diflieulties. Drying at this temperature, however, might be expected to be a slow operation, since the cellulose material would be likely to hold moisture in a rather retentive manner. However, there appears to be a relation between the period of heating of the initial reaction mixture to that of drying. If the reaction is carried forward in the liquid stage, that is the initial stage, as far as is possible consistent with molding requirements, the escape of water from the composition in the -lryers is more rapid than when the reaction has not been carried so far. Apparently there is a condition akin to casehardening when the reaction has been less advanced in the liquid stage and pushing the temperature to an elevated point in order to force out the moisture only aggravates this condition and as a result by the time the product is well dried it has becomepre-cured and will not flow freely. The present invention, therefore, contemplates carrying forward to its reasonable limitations the initial heating in the liquid stage and then preferably drying at a very moderate temperature. In this way products having remarkable qualities of flow in the mold, coupled with rapid curing, are obtained.
i lvo'idancc 0f dvlscolofing metals Molded products of the character obtainable in accordance with .the present invention have the advantage over those made from phenol formaldehyde resins, and the like, of their light color or colorlessness, with the result- N Cooling the reaction mimtara-0n the' large scale a reaction receptacle may be provided with a coil through which a heating or cooling fluid may be introduced. For example, steam may be passed through in order to heat the mixture and then, if the reaction becomes too violent, cold water may be passed through these same coils to check the turbulence of the reaction.
Incorporation with ceZZuZ0se.--As stated in several of my prior applications, cellulose in its various forms may be employed, including the crude form, such as ground wood or wood flour, and more purified forms of cellulose, such as paper, cotton'fiock, linters, and the like. A suitably purified form of paper is alpha cellulose in sheet form. In ineorporating cellulose with the syrup care,
should be taken to have present enough water to permit allwthe fibres of the cellulose to be ably the syrup, diluted with water or undiluted, as the case may be, is mixed while hot with the cellulose. The latter preferably is also heated'prior to introduction into the syrup. Thorough impregnation is important in order to secure that change in the character of the cellulose which results in the production on hot pressing of translucent articles.
impregnation by a vacuum and pressure.- Impregnation of cellulose fibre may be conducted by a vacuum and pressure process, that is, the fibre as such or in paper form or otherwise is placed in a closed receptacle and the air withdrawn to produce a high vacuum. The urea resin impregnating syrup then is run into the receptacle and pressure is applied. In this way the fibres are better impregnated. This is desirable in particular, as stated in Serial 742,719 (page 5, second paragraph) when paper of some thickness is used. Impregnation adequate to fill the canals of the fibres in a substantially complete manner tends 'to yield the highest degree of transparency or translucency in the finished molded article or laminated sheet. A vacuum of, for example, 20-25 inches or thereabouts of mercury may be employed followed by a pressure of 50-100 lbs. or higher, as desired.
Introduction of colom'nn wwtefials.0w-
ing to the colorless character of the product if made according to the foregoing directions, only a small amount of a dye is required to create. a strong coloring effect. For example, from a half gram to one gram of a dye such as rhodamine suflices to strongly color from 5 to 10 kilos of the composition. Soluble dyes may be added to the syrup before it is reacted with the cellulose material. Mineral pigments may be incorporated with the dried composition during ball mill grinding, if this step is carried out. 'hen the syrup has been made with the aid of thiourea or similar sulphur resins, care should be taken not to use a pigment which reacts with sulphur to cause an undesirable change in color.
Drying the c0mpos-Zti0n.If the filler is in sheet form as, for example, alpha cellulose, impregnation may be conducted, for example, by passing the dry sheets through the hot syrup. If the cellulose is in loose tibrous form, it is stirred thoroughly with the hot syrup andthe product in either case is pref erably dried at a temperature ranging from 4075 (1., the manner which I have already indicated being suitable. In Serial ($89,105 (page 7, line 3 from bottom) I have proposed drying at room temperatures and at higher temperatures ranging from Fifi-(30 C. In the same application vacuum drying up to 50 C. is disclosed (page 24-, line 18). In
some cases higher temperatures .are employed as, for example, (page 24, line 15) drying is carried out in a vacuum dryer. In that particular instance, however, the overcuring resulted under the conditions of preparation of the material. Clear glasslike material has been obtained by vacuum drying up to a temperature of 90 C. (Serial 689,165, page 23, line 7). \Vith an asbestos fibre filler (same specification, page 24, line 9) vacuum drying up to 90 C. Was employed. In Serial ($04,420 (page 7, line 17) drying was carried out by exposure at 90 C. in a vacuum dryer for one hour, until the mass had a crisp and brittle feel. In the latter instance the syrup was incorporated I fine, or at least the coarse lumps of matted material coming from the dryer should be broken up. A suitable procedure is to place the dried charge in a ball mill, which has no interior parts of iron or other discoloring metal, and grinding until the composition has been reduced to a stage of fineness such that it will pass a 40 mesh sieve. A good determination of the degree of drying can be secured by a preliminary test. ina small way in a ball mill. If drying has been carried through to a stage where the product has a crisp feel, grinding will take place readily and the product, other things being carried out properly in accordance with the foregoing, will mold nicely. If the drying has been inadequate, the moisture present may tend to cause lumping and imperfect grinding. In such case the material should be placed again in the dryers and the moisture removed. The quality of grinding, therefore, is to a very considerable extent an index of the degree of drying and when one is inexperienced in making the material and cannot judge readily by the feel of the dried composition whether or not it is sufficiently moisture-free, a'ball mill test may be employed. \Vhile I have specified a product passing a 4-0 mesh sieve, I may employ finer or coarser gradations, as desired. Of course, when 'the product is to be handled in sheet form grinding will not be required.
Introduction of mold lubricant. During the grinding pigments and mold lubricants may be introduced. For light colors a suitable mold lubricant is zinc stearate, although other insoluble metallic soaps such, for example, as aluminum palmitate, may be used in certain cases. In general, however, a metallo-organic lubricant should be used which has no discoloring effect and zinc calcium or magnesium soaps in finely powdered or precipitated form may be used advantageously. From one-half per cent to one per cent of zinc stearate may be added to the charge in the ball mill. Other mold lubricants, such as stearic acid, wax, and the like, may be employed in special cases. For
reference to the use of mold lubricants see Serial 742,710 (page 5, third paragraph). Introduction of metallic soaps tends to reduce translucency; In some cases 2 or 3 per cent or more of zinc stearate may be added to yield an opaque molded product which may be given a tint to resemble ivory. However, translucency is a highly important property and any additions which tend to reduce it are undesirable. For this reason metallic soaps if used should be employed in minimum amounts so as to impair translucency as little as possible.
rl/ old/'21 ])7'(.s.s'1 7"('.s".I he composition then is ready for molding, which may be conducted by means of charging the material into the cavities of plunger molds and submitting to hot-pressing. In molding the compositions of the type specified herein I find a certain range of pressures yields shaped products of goods definition and surface finish. Serial 089,165 (page 13, line 19) specifics a presssure of 1,000 lbs. or higher (ranging to 3,000 lbs.; see page 24, line21'; note also Serial 28,505, page 13, line 1). This same range is set forth in Serial 694,420 (page 3, line 3) as a pressure of one thousand to two or three thousand pounds. The precise pressure selected within this preferred range will depend on the flowability .of the composition. Thus in Serial 735,600 (page 3, line 13) a pressure of 2,000 lbs. is used in an illustrative example, while in Serial 742,719 (page 5, line 11) 3,000 lbs. is used illustratively for forming laminated sheets. The preferred pressure range therefore ext-ends from one ton to one and one-half tons per square inch of mold surface and this pressure should ordinarily be indicated by a gage on the press. There are conditions where a departure from this preferred range may be required, especially in the direction of higher pressures for certain resistant compositions, particularly those having a high content of special fillers.
Temperature of m0ZcZing.Unlike phenol formaldehyde resinous plastics which are capable of being subjected to relatively high temperatures without disturbance, the molding compositions made with the urea type of resins are notably sensitive to temperatures above a certain relatively low limiting point. In order to cure phenol formaldehyde resinous compositions as rapidly as possible, it has become customary to mold at fairly high temperatures, ordinarily too high for the urea resin plastics. As a result of the technique which has developed in the phenol formaldehyde plastics, operators familiar therewith are liable to overheat the urea resin plastics and condemn them because of the surface imperfections resulting from such overheating. Throughout my earlier applications I have pointed out the danger of blistering and disintegration unless the molding operation was carried out below such limiting or maximum temperatures. On the other hand, ouring is too slow when molding is carried out at an inordinately low temperature. More over the rate of transmission of heat to the mold should be considered. Temperatures registered by electrically heated platens usually should range between 100 or 110 (111p to about 150 C. A good optimum temperature range is between 125 and 140 C. In molding with steam heated platens the transmission of heat is usually slower and misleading results are returned if the as-- in Serial 694,420 a temperature of 120 C. is used in one case (page 7). In another case 130 C. is used as a maximum (page 8), this being a desirable maximum for products in which whiteness or lightness of color is to be effectively preserved and elsewhere a temperature of 150 C. is mentioned (page 11). Likewise in the production of laminated material, as set forth in Serial 742,719, temperatures of 120130 C. are recorded (pages 5 and 6) See also Serial 28,505.
Avoidance of bZisterz'ng.-In Serial 694,420 (page 11, line 6 and page 12, line 10) I call attention to the effect which the presence of cellulose imparts of greatly reducing blistering tendencies. which the introduction of wood flour (with or without a white pigment or other pigment material) reduces the tendency to blistering. This and other effects which have been prevlously recorded by me indicate an action by the cellulose material to be something more than that solely of the role of a mere extending agent or filler. thIf mechanicalbwaterfis well removed from ecomposition care ull dr in u to sa 75 C., asubst antial prbpoi tioi (Ff cbllii lose (at least 25 per cent of the composition) has been used and the preferred maximum of 150 C. molding temperature is not exceeded, blistering difficulties are unlikely. Water which may be present in the mold and become converted into steam with formation of blisters is in part due to the reaction of condensation which may liberate water during the thermo-setting. Such water may be termed latent water. While mechanical water may be removed by drying, the latent water liberated in the mold cannot be readily freed from the molded article except that part which is liberated near the surfaces of such articles. The cellulose material, especially hydrocellulose, is useful in absorbing latent water. Thus a hydrocellulose cellulos'ate which may have become considerably dehydrated during drying can become more or less rehydrated during hot pressing due. to absorption of latent water of condensation. This, the-refore,-in a sense is merely a transfer of water.
Breathing the mold-When a composition contains more than a certain proportion of mechanical water, molding will be difiicult unless the plunger of the mold is raised once or twice during the pressing to allow the escape of steam. This is especially noticed in the case of urea resin alone, without thiourea condensation products. The step of releasing the mold in this manner is termed breathing the mold. It is not a desirable step, since it constitutes one more operation to receive attention and should be avoided if possible.
Spraying with wuter.On the other hand,
Therein I note the manner in there are certain cases where the addition of water is helpful in improving flow. Compositions which have been overheated during the drying, or for other reasons do not flow freely, may sometimes be improved in flowing qualities by very slightly moistening with water as, for example, by atomizing water into the pulverzied material while the latter is being agitated. In this way a rather low grade product may be obtained which can be used for purposes not requiring a high quality product. It should not be inferred from this statement, however, that such a procedure of moistening is desirable. It is only a makeshift which sometimes can be employed.
Duration of curing in the m07d.The cur-- ing time should be rendered as brief as possible. For thin moldings a molding time of from 2 to 5 minutes is desired. For thicker articles up to 10 minutes, or even longer, may be needed. The composition, therefore, should be as heat sensitive as is feasible consistent with adequate flow. Sometimes it is desirable to add to the composition a catalyst.
which will speed up the curing time.
Owing cataZy sts.As noted in the foregoing, acceleration of curing by the addition of catalysts sometimes may be required. These may be direct acting, that is capable of exerting acceleration of reaction at all times, or they may be latent, that is active only when a given temperature is reached. In Serial 694,420 (page 8) I have noted that rapidity of molding is a very important consideration owing to the high labor cost of such manipulation. Hence any procedure which will shorten the time the composition is taking its final shape in the mold is of importance. With white articles sensitive to higher temperatures than those specified, the duration of molding may be adjusted or accelerated by the presence of an acid catalyst present in an amount adequate to meet the particular requirements. Likewise in Serial 689,165 (page 11; see also Serial 28,505, page 10, second paragraph) I have pointed out that sometimes it is desirable to carry out the initial reaction between urea and formaldehyde, paraform or other aldehyde employed, in an alkaline medium to the point where particles begin to precipitate and that instant to arrest the action by the addition of acetic or other acid to approximate neutrality. If the alkali is allowed to react beyond a certain point the reaction batch may solidify to a magma or white pasty substance which cannot be used advantageously for casting, although it may be dried out and used in hot-pressing. Therefore, before the liquid starts to thicken with separation of the reaction product, it is neutralized. Thereupon an acid catalyst may be added in such proportion, with or without cooling,
as may be desired with reference to the speed of setting. Citric and oxalic acid, phthalic anhydride and other acid bodies mentioned in my prior applications may be used for the purpose. In some cases urea phthalate,
and the like, may be employed. As latent catalysts there may be mentioned some of the amine hydrochlorides, also various salts of alkyl sulphuric acid, e. g., sodium or barium ethyl sulphate which decomposes at 120 G. into ethyl alcohol and sodium bisulphate. The latter is active accelerator of hardening. The proportion of catalyst may range from less than 1/100 of a per cent up to several per cent. In some cases fluxing catalysts may be used, that is bodies which tend to have a fiuxing effect in the first instance and then as the temperature of the mass in the press increases a breakdown occurs with liberation of catalytic material.
Translucency.-Ayery important feature of articles made from cellulose and these urea condensation products is their translucency. This is a quality which hitherto has been difficult to secure in non-inflammable plastic material of relatively low cost. Transluceny may be aided by thorough incorporation of cellulose and the urea syrup, pr ferably allowing adequate time for the hot solution to react with the fibre. Drying, moreover, should be thorough. Mineral pigments should be absent, in their place soluble dyes being used. As already noted under lubricants, the presence of more than a very small percentage of zinc stcarate tends to decrease the translucency. Another method of improving translucency is to use fairly high pressures during molding, as, for example, 2,0003,000 lbs. Higher pressure possibly brings about further reaction between cellulose and the urea material to form more fully reacted cellulosates, thereby increasing translucency.
Opacity .On the other hand, when opaque products are desired the addition of a few percent of a mineral pigment sufiices. If a white article is desired a number of the white mineral pigments are available, particularly those which are not discolored by sulphur (this consideration applying if a sulphur resin is present). Pure titanium dioxide, or its commercial embodiment known as titanox, is a useful white pigment and may be used in conjunction with the cellulose in various proportions. .Lithopone is even better in some respects. In no case does it appear necessary to employ more titanox than corresponds to equal proportions by Weight of this titanium pigment and cellulose. In the majority of cases a considerably lower proportion of the mineral pigment suffices. This is notably true when the pigment possesses a strong pigmenting power.
Molding then baking-In Serial 694,420 (page 8, line 11) I have disclosed the step of hot molding, followed by a baking or stoving treatment. The composition can be given a-preliminary rapid molding and the shaped article in a semi-cured condition is thenplaced in. an oven and subjected to a -'baking temperature, for example, 100 C.,
. for aperiod of two or three hours.
A baking range of 60100 C; is therefore permissible, but care should be taken that the baking oven is not too hot when the semi-cured articles are first placed therein, other-wise warping may ensue. The danger of warping is reduced with the degree of hot pressing. That is, if curing has advanced to a very considerable extent in the mold, warping in the baking ovenis not likely to occur. Therefore the most careful watch should be.
taken with only slightly cured pressed articles, as these are more sensitive to warping and therefore will require initially a corre spondingly lower bakingtemperature.
Laminated sheets 01' masses.By hot pressing sheets of impregnated paper or pulp, laminated sheets .or other articles may be produced. Procedures of this character have been fully described in my co-pending application Serial 742,719. In that specification I have described how thin paper, such as tissue, parchment, rice paper, crepe paper and a calendered paper known as glassine, commercially used in the manufacture of envelopes displaying the address through an aperture on the face thereof.
The laminated material may take th form of plain press-board or by using alternating layers of different colors a thick sheet or block may be built up which if desired may be cut into various shapes, the cut edges of which will show alternating colors.
In making the laminated material it is possible also to insert photographs or pictures which, provided the pressing is carefully done, may be embedded in the sheet and thus protected.
In other cases metal flakes or powder such as gold flakes or aluminum powder may be scattered through the laminations. Again strips of the treated paper may be Wound on a mandrel to form a cylinder, cone, and the like, and the mass subsequently pressed in the manner to be described.
A particular feature of the present invention is the production of sheets which even though of considerable thickness will transmit light. Thin layers are practically transparent and the thicker layers are of an opaqueness ranging from that of frosted or ground glass to a higher degree of opacity.
In one form of the invention I may take clippings or shreddings of the treated tissue or other paper and compact them by hot-' pressing to produce a striated molded article, sheet or block. When these clippings are made from paper that has been dyed in different colors, a multi-colored effect 'is obtained by mixing he shreddings of different colors and hot pressing.
Furthermore, it is possible to take portions of the shreddings and place in different parts ofthe mold so that .thecolors in a given sheet, block or molded piece. will be segregated.
In carrying out the molding or hot pressing of such material, the shreddings may first be tableted if desired and then molded at the requisite temperature.- The molds may have surfaces which give an embossed effect or print in raised or depressed letters any desired name or emblem. In some cases fillers may be incorporated with the paper sheets.
Veneering.In the same category as laminations are included veneered products made by hot-pressing a'facing on a heavier or stiti'- er backing or support. The latter may be, for example Wall board in anyof its forms or other thick supports of pulp, and the like, including slate, glass, wood, but in particular any material capable of withstanding the mechanical and temperature stresses arising in the operation. Sheet metal or other metal supports may be used in some cases. The sup;- port frequently is a plastic of itself andmay', in some cases, be of the urea resin type. Thus a plastic may be made from urea resin or urea-thiourea resin, or other modifying resin, incorporated with a relatively high proportion of wood flour, wood raspings, wood chips, sawdust, or mixtures of these. Preferably I employ in such backing composition at least 50 per cent of thecellulosic material and more often from 60 to 80 per cent thereof. I have been able to use wood flour made from sbft Wood in the proportion of per cent of the latter to 25 per cent'of the resin solids and have, in some cases even exceeded that proportion. When hard wood of'greater density is used, even higher proportions are possible. Using a light colored Wood flour, the resulting molding, if pigment has not been added, will normally be of'a brownish color, more or less translucent. The high proportion of cellulose usually does not per- Thus for such backings I i Using such material as the backing, I may provide a surfacing material consisting of a number of sheets of impregnated tissue paper prepared. for example, as set forth in Serial 742,719. or I may use a single, rather heavy sheet of light colored cellulose, such as alpha cellulose. The thickness may be as required according to the desired depth of veneer. The
sheet of material may be suitably colored On its upper means of dyes or pigments. side a very small percentage of zinc st-eara-te maybe included in order to allow the pressed surfaces to be readily released from the mold. The well-dried sheeting suitably prepared. while hard and crisp at room temperature, shows plasticity at. say, 60 C., so that the sheets can be bent. over shaped pieces or rounded or bevelled edges of a support. When the supporting structure is ofsteel and adhesion thereto is desired. the steel or other metal therefore should be well cleaned. Zinc stcarate or other mold lubricant preferably should not be present on the under side of theimpregnated paperwhich is to contact with the metal formor support.
Vcnocrin 7 7n'o0crlure.Difterent steps may be adopted. depending on the precise result desired. In one case. for example. impregnated alpha cellulose in sheet form is laid in the bottom of a fiat mold. e.'g.. a panel mold. and over this is spread to considerable depth a backing composition in powdered form made from urea resin (or urea-thiourea resin) and ground wood in high proportion. The mold cavity thus having been filled with the charge. hot-pressing is conducted to weld all together. In this way a backing perhaps ,4 to ,4 inch in thickness may be surfaced with a veneer to inch in thickness. The alpha cellulose or snlphite fibre sheet may. as indicated. be tinted to any desired color and if dyes are used instead of mineral pigments the result is a decorative translucent veneered effect wholly covering the brown colored. but strong and rigid backing. Such veneered sheets. panels. and other shapes. may
be made relatively cheaply and have many prospective uses.
Another method of veneering is to place the powdered con'iposition in the mold and hot-press to form a partially cured backing. On this place a sheet of alpha cellulose and again press to complete the curing of the backing and to cement the cellulose veneer in place. \Vhen desired. special designs may be prepared by cut-outs of different shapes which can be laid on the surface of the backing to fit nicely as, for example. like parts of a jig saw puzzle and when these multicolored pieces of the veneer or material are pressed there may be obtained various futuristic or other designs as desired.
Tiles suitable fo" bathrooms, and the like, may be made in this way or by any other veneering procedure within the scope of the present invention.
Shaped oeneer.It is proposed to manufacture various bulky articles, such as lamp bases, urns and heavy decorative bodies, chair backs, arms, rungs, legs, and other furniture parts or requirements, bathroom equipment, and so forth, by preparing a shaped base or form of relatively cheap material and laying over this an impregnated sheet as described above, suitably colored. The sheet is warmed sufficiently to become plastic so it may be bent or wrapped about all or such part of the form as is required. Then the wrapped form is placed in a hot-press having a mold to correspond and the veneer is thereby pressed and shaped into place to conform to the base and to give the latter a decorative finish.
Plunger 'vencering.'lhis step may be illustrated by the method of covering a tapering chair leg, square in cross section, with a veneer of plastic composition as aforesaid. A mold cavity is provided slightly larger than the chair leg and the molding composition placed therein. Then the leg is forced into the composition while the latter is being heated, thereby to form a veneering finish.
E mtr'usion.Rods, tubes, chair legs and rungs, pipes for liquids, and the like, may be prepared by extrusion downward from a suitable die of the foregoing plastic. This treatment may be followed by cautious baking, if desired. The same procedure of extrusion may be utilized to form elongated masses shaped like boards or planks.
FZum'n-g.For extrusion purposes or possibly in other cases, when a more plastic material is required, there may be added various fluxes, such as glycerine, glycol, diethylcne glycol, and so forth. In some *ases tl addition of 2 or 3 per cent of thiourea. in the charge when it is being ground in a ball mill serves to bring about adequate lluxing.
Incorporation of other resins and plastic bodies-In the foregoing I have referred to various modifying resins, such as phenol aldehyde resin, acetone aldehyde resin, sulphur phenol resin, and others. Various proteids, as indicated in my prior applications, may be used as modifying agents, including casein, glue and gelatine, Irish moss. algin, albumin, dried blood, and the like. These may be used in all proportions and therefore it is not necessary to set forth any specific formula. Vinyl resins, being capable of production of a light color, may be used in some cases with the light colored urea resins to yield various products such as those described above in which the vinyl resin exerts a modifying influence. By urea resin I include also urea-thiourea resin, and the like.
Water resistance-Tiles and many other articles, such as bathroom equipment, must exhibit Water resistance and for this purpose it is desirable to use thiourea in conjunction with urea. The higher the proportion of i thiourea the more positive the water resistance. It is, however, not necessary to go beyond a certain proportion in order to secure sufiicient water resistance for all practical purposes. Thiourea is more costly than urea and therefore should be used in as low a proportion possible consistent with meeting commercial requirements. Even as low as 1 part of thiourea to 9 parts of urea has a considerable influence on the. action of moisture. While a composition made from urea formaldehyde resin alone will give molded articles which in the course of time lose their glossy finish, due to action of moisture, the same compositions in which, however, thiourea has replaced the urea to the extent of 10 to 20 per cent hold the finish in much more durable manner. For most purposes a proportion of thiourea to urea is the maximum required ofthis more expensive ingredient.
Printing bZ00ks.Using the plastic of the present invention I may make printing blocks or printing plates which may be molded d1- rectl from the original as a matrix. Such mol ed printing blocks may, if necessary, be hardened further by baking. Such blocks may be required to stand pressures of 450 lbs. per square inch. Type metal Wlll stand onl about 300 lbs. 1
b accessz'oe additions of ceZZuZ0se.-A procedure of significance from the manufacturing standpoint is the two-stage or multi-stage addition or incorporation of cellulose, such as alpha cellulose, cotton flock, linters, and especially ligniform material such as ground wood or Wood flour. When compositions are made containing a relatively high proportion of cellulose, there is obtained a great bulk of material requirin a considerable time to dry thoroughly. When the cellulose has been thoroughly wetted with the urea syrup, as the latter dries it goes through a gelatinous stage 'with possible difficulties from case-hardening or incrustation preventing thorough drying. If the temperature is raised to create a relatively strong heat, there is danger that the resin will become precured. It is possible, however, to incorporate only part of the cellulose, using just enough to act as an absorbent for the syrup, e.-g., to a syrup containing parts total resin solids use 40 parts of wood flour. By thus using in substantially absorbing proportions or preferably optimum absorbing proportions, there is only a moderate mass of material (relatively considered) to be dried. After drying and preferably when incorporating pigments, mold lubricants, and the like, in the ball mill, there may be added at any suitable stage, but preferably after the impregnated cellulose has been ground, an additional quantity of the cellulose material which is unimpregnated, that is, the normal fibre or ground up wood stock. A thorough mixing is made of the impregnated and u nimpre ball mill mixing and grinding or by running through'a comminuter. The initial charge or absorbing ortion of the cellulose ma be called the prlmary cellulose and: that which is added to the dry unimpregnated material at a later stage ma be termed the sequential or secondary cellu ose- Thus to an impregnatd batch made in the proportion of 40 partscellulose to 60 parts of the dry solids of the urea syrup there may be added an equal amount, i. e., 100 parts of wood flour as the sequential or secondary cellulose. Thus there would be --obtained a mixture in which 40 parts of wood flour impregnated with 60 parts of the resin were mixed with 100 parts of unimpregnated wood flour sequentially added, giving a finished molding composition with 30 per cent urea binded to per cent wood flour. Similarly there may be added as the sequential charge 125, 150, 200 or 300 parts wood flour, giving percentages of the latter reckoned 1n the finished molding composition as about 27%, 24%, 20% and 15%, respectively.
Disappearance of Zignifom structure. As I have indicatedin certain of my co-pending applications, there appears to be, to some extent at least, a solution or absorption of cellulose by the resinified urea material when the reaction of hardening or curing is allowed to take place under-heat and pressure. In
any event, there is to the eye adisappearance of fibre to some extent which constitutes virtually a delignification. Wood flour with its component of lignin appears to be especially useful in this respect, which may be due in part to the presence of the lignin. When additions of wood flour substantially beyond the absorptive capacity of the urea component are employed there may be obtained after pressing articles somewhat resembling wood which may-be used as artificial lumber.
Addition of catabyst to the sequential cel lalose charge.After drying the composition with its primary charge of cellulose, the introduction of the secondary or sequential charge of cellulose to the dry batch permits of the addition of catalysts in a disseminated form, i. e., distributed in the pores of the particles of the sequential charge. Thus an acid catalyst, such as boric, phosphoric, phosphomolybdic, silicotungstic, or other mineral acid or acid salts, e. g., bisulphates, alum, zinc chloride, and the like, alkyl sulphuric acid, various organic acids, such as formic, acetic, trichloracetic, lactic, citric, tartaric, succinic, phthalic, salicylic acids (or their anhydrides, as the case may be), singly or in admixture, dissolved in water or other appropriate solvent, and the sequential charge of, for example, wood flour is wetted with the solution. Each particle of the wood flour thereby receives its quota of the catalyst.
gnated cellulse either, as indicated, by i The latter then is air-dried or heated as may be required to remove moisture or solvent. Volatile acids such as formic and acetic acids, although mentioned in the foregoing, are not considered as suitable because the cellulose material cannot be as thoroughly dried with out volatilization of a part of such acids. The sequential charge of cellulose if thoroughly dried serves an important function with respect to prevention of blistering, as will be noted later.
Acidulated wood flour catalyst.Wood flour varies with the grade of the wood, depending on whether pine, spruce, fir, and the like are employed in its roduction. Cedar sawdust or cedar wood our has characteristics different from the aforesaid woods. Sometimes harder woods may be used; likewise ground bark, such as that of the sequoia. The proportions therefore in both the primary and the secondary charges will vary with respect to the absorbent character and other properties of the cellulose material.
Any of these, however, may be charged with a specific hardening catalyst, usually of an acid character, although in some cases of an alkaline nature to render the whole catalytic in bringing about rapid curing in the mold. If the catalyst is introduced in this way it does not come into active contact with the urea resin binder until the latter is molded under the heat and pressure of the mold. Different types of cellulose may be used for the primary and for the secondary charge. For example, a very finely ground pine wood may be used as the absorbent charge and cedar sawdust or flour used as the secondary charge.
Bone-dry secondary cellulose-When the urea resin material is reacted under heat and pressure to cure it, a certain amount of volatile material, principally the latent water of reaction, is liberated. There is also usually present some mechanical water which has not been thrown off completely in the drying step. This water may be a disturbing factor in the mold, causing blistering. The difficulty is especially noticeable with urea formaldehyde resin, that made from urea-thiourea formaldehyde being less likely to blister. However,
troubles arise in both cases. Breathing the mold is one way of avoiding blistering, but it is an operation which should be avoided if possible and is not always a certain remedy.
y using a secondary charge of wood flour which has been heated thoroughly to render it quite dry the composition acquires a high proportion of the water absorbent. The absorption by the bone-dry wood flour of that amount of moisture which normally would be present sufiices to take up all water otherwise creating disturbing conditions in the mold and this compensation of water evolution allows the production of smooth, well molded articles, free from blistering.
A considerable number of illustrations are hereinafter given in which the same ratio of urea, thiourea and formaldehyde is maintained. This is illustrative in that it affords a desirable basis for comparison. However, by using these stated proportions for comparative purposes I do not wish thereby to limit myself either to proportions or to the precise character of the raw materials, it being understood that I may make combinations and additions in various ways and with various materials within the scope of the invention.
In the illustrative examples the proportions given are parts by weight.
Example 1.-Urea 840 parts, thiourea 300 parts, aqueous formaldehyde solution (formalin) 2400 parts. The solution contained 37.1 per cent actual formaldehyde and was used in practically neutral form with pH 5.6.
The urea and formaldehyde solution was mixed in the cold and heated under a reflux condenser to boiling point. Boiling was continued for 10 minutes, the temperature under these conditions being approximately 97.5 C. At the end of 10 minutes the thiourea was added and the boiling continued for a total period of minutes. The hot solution was poured onto 730 parts of wood flour (the latter passing 20 mesh sieve). After being well mixed the wet mass was dried by spreading out on screens of Monel metal placed in a drying chamber through which a gentle current of air was passed, the temperature ranging from 30 up to 52 C. Drying was continued until the lumps of the material had a brittle feel and could be readily crushed or ground in a ball mill. At this stage drying was considered complete and the batch was placed in a ball mill where it was ground for a period of about 1 hour until fine enough to pass a mesh sieve.
This molding composition was then tested for its molding properties by conducting pressings at 1500 lbs. pressure per square inch and temperatures of the mold ranging from 100 to 130 C. The product possessed an extremely good flow and yielded light brown shaped articles of a very attractive translucent appearance. Some of these specimens were pressed only to a semi-cured stage and then were baked for 3 days at a temperature of 65 C.
Example 2.The same proportions of raw materials were followed, the pH of the neutral formalin solution being 5.4 and the reaction at the boiling temperature being continued for a total of minutes. 1280 parts of wood flour of relatively long fibre were used. This product after drying and grinding in the ball mill was found to mold nicely in the hot press at a temperature of 115 C. employing a curing time of 6 minutes and a pressure of 1500 lbs. Some of the specimens made in this way were subsequently baked at C.
Example 3.-This molding composition contains a much higher roportion of wood flour. The conditions were much the, same as in Examplesl and 2, the same quantities of raw materials being used, the formaldehyde solution having a pH of 5.23 and the boiling being carried out for minutes. The clear syrupy solution thus obtained was mixed with wood flour'and drying and grinding carried out in the same manner. The flow of this composition was not quite as free as that observed in the case of Examples 1 and 2, but was adequateand enabled fairly good molded specimens to be obtained by hot pressing at 115 Q. under a pressure of 1500 lbs.
E :rample 4.'-Using the same quantities of urea, thiourca and formaldehyde solution, the latter being in the zone of neutrahty with a pH of 5.3. A reaction period of boiling for minutes yielded a syrupy solution WlllCll was divided into three parts. To one part there was added 10 per cent of wood'flour based on the total solids in the solution. To another portion there was added 25 per cent of wood flour, while the third portion received no addition of wood flour. These three portions were all dried in a vacuum oven at a temperature of about C. until sufficiently dry for molding. After dryingand grinding, pressing tests were conducted to determine which portion cured to best advantage. It was found that without the cellulose (wood flour) material the resin was too easily liquefied and too slow in curing to be employed easily in molds having normal clearances.
On hot pressing the resin exuded from the mold to such an extent that the production of a good molded specimen of the required dimensions was impossible. The portion containing 10 per cent of cellulose molded to better advantage, showing much less exudation and moderately good curing properties. There was, however, a slight degree of blistering observed. The portion containing 25 per cent of cellulose cured nicely in the mold without blistering and furnished excellent molded specimens.
E trample 5.The same quantities of urea,
thiourea and formaldehyde solution were used as in Example 1, the pH of the formaldehyde solution being 5.3 and the boiling period of reaction being 25 minutes. lVith the same quantities as employed in Example 1 the resulting syrup was used to impregnate 812 parts of alpha cellulose in sheet form. This was carried out by passing the sheets through the solution. Prior to such immersion at small amount of dye, namely ,4 part of rhodamine, had been added to the syrup thereby causing the cellulose sheet to become dyed a strong pink. Approximately 1600 parts of the finished sheet stock was thus derived. I
E trample 6.In Example 5 the alpha cellulose sheet in dry form was impregnated ing to its more spongy or stringy character was obtained. From the standpoint of ease of grinding, therefore, it is better to impregnate the cellulose stock when it is dry rather than when it has been first converted into a pulp with water. Aside from the somewhat greater difliculty of grinding, there is the further possibility that a highly flocculent or voluminous material is not as easy to mold. The amount of charge which can be placed in a given cavity is less and larger molds,
therefore, have to be constructed. Densification of the molded material, therefore, is desirable and if this can be secured'as a part of the normal manufacturing procedure the extra step of tableting is avoided, at least in the majority of cases. Of course, when a multi-colored molded article is required which is to be secured by placing in the mold tablets of different colors, the procedure of pre-forming or tableting may be utilized.
Emample 7.The alpha cellulose stock dries rather slowly when made in accordance with the procedure of Example 6. To shorten the time of drying the reaction mixture was boiled for a total period of 50 minutes. It was then found to dry in approximately half the time required when the reaction was carried on for only 25 or 30 minutes.
Ewample 8.A batch.of syrup was made in a manner similar to Example 6, but the boiling was carried on for 80 minutes to form a more viscous syrup. A portion of the syrup was-withdrawn and used for the impregnation of alpha cellulose. 130 parts of this stock were used to absorb about 400 parts of the syrup, thereby taking up in the fibre approximately 260 parts of the resin on a. dry basis. The remaining portion of the syrup was boiled until the total time of heating was 100 minutes. A sheet of alpha cellulose 52 parts absorbed 160 parts of the reaction mixture, calculated on dry weight.
Emample 9.Using 840 parts urea, 300 parts thiourea and 2100 parts of formalin, the pH of the reaction mixture being within the neutral zone, namely, 5.3, the reaction was carried through a period of 50 minutes total time of boiling. A small amount of sulphur rhodamine dye was added and alpha cellulose sheet stock was run through the hot syrup. The absorption which took place yielded an impregnated material containing approximately 33 per cent of cellulose. This was dried slowly between 40 and 50 C. until hard and crisp.
Example 10.The weights used were the same as in Example 9, but the formalin was diluted with 6 volumes of water. The pH value was 0 and the boiling conducted for 60 minutes. 800 parts of Wood flour having a long fibre were used to yield (calculated on the dry weight) approximately 7 5 per cent of the cellulose material. When this had been thoroughly dried a small amount of zinc stearate was added and thoroughly mixed in a ball mill. Grinding in the ball mill was not as complete as when fine wood flour is used, because the longer fibered material is more elastic and springy. This material was found to mold well under hot-pressing at 125 C. When molded at 3,000 lbs. pressure a good bit of reaction seemed to take place in the mold with the resulting absor tlon, solution or disappearance of fibre. ncreasing the pressure under these circumstances aids such conversion or apparent change and the pressure, if desired, may be raised to 4,500 lbs. or higher in order to favor the change.
E wample 11.-A sheet of the impregnated alpha cellulose according to Example 9 was placed in the bottom of a mold and the high cellulosic product of Example 10, in powdered form, was charged into the mold above this sheet. On hot-pressing a rigid, panellike product was secured, the thick and rigid backing of which was of a brownish color while the face was of a clear, translucent, pink shade.
Example ]2.84.0 parts urea, 300 parts thiourea and 2250 parts formalin solution were used. In this case note that the proportion of the latter is reduced over that employed in the previous examples. The pH was 7.2 and the boiling conducted for 30 minutes. A fine grade of wood flour was incorporated with the syrup to yield approximately 36 per cent cellulose material based on the dry weight. On drying overnight at about 60 C. a crisp product was obtained which ground readily in the ball mill. Prior to drying, however, the batch was separated into two parts, to one of which was added a solution of barium ethyl sulphate equivalent to approximately 1 per cent of the dry weight.
The product containing the latent catalyzer when molded at 140 C. and higher gave shaped articles which showed excellent resistance to boiling water. A product of this kind can be used to make various molded articles as such or employed as backing or su ort for cellulose sheet veneer.
wample 13.The same proportions and quantities were used as in Example 12, with the addition of 10 parts of light ma esium carbonate. The initial pH was 7. y 11 heating gradually over a period of 10 or 12 minutes the pH was'found to be 8.4 (the temperature then registering 65 (1). A boilmg temperature was reached in 17 minutes, the pH registering 7.8. Thiourea was added and this required about 10 minutes to dissolve, being completely in solution 37 minutes from the time of starting the heating. The pH recorded 'at that time was 7.7. At the end of another 10 minutes, or 47 minutes in all from beginning of'heating, the pH registering 7.6, 1,000 parts of fine wood flour were added. The composition was dried, ground in a ball mill with the addition of a small amount of zinc stearate. This composition was found to flow extremely well on hot-pressing. A portion of the product treated in the ball mill was moistened with water (with and without addition of catalyst), and dried. The product was found to have agglomerated into granules of notably greater density and compactness than the material coming from the ball mill. This granulated product is useful in molding operations where a substantial charge, without undue bulk, has to be introduced into the mold.
Example 14.The syrupy products obtained in the course of preparation of the foregoing compositions may be used as a glue for cementing Wood veneer to its support, or for making laminated wood products. Thus the syrup obtained in Example 13 may be applied to one side of the sheet or veneer and this sheet glued onto a wooden support. In this way, while the veneered surface is wood, nevertheless the urea composition forms a part of such veneer and therefore is included within the scope of the present invention.
1. A molding composition comprising a thermo-setting resin of the urea type carried as an impregnum in finely divided cellulose and incorporated with unimpregnated cellulose.
2. A molding composition comprising a thermo-setting resin of the urea-thiourea type carried as an impregnum in finely divided cellulose and incorporated with unimpregnated cellulose.
3. A molding composition comprising a thermo-setting resin of the urea type carried as an impregnum in finely divided wood flour and incorporated with unimpregnated wood flour.
4. A molding composition comprising a thermo-setting resin of the urea-thiourea type carried as an impregnum in finely divided wood flour and incorporated with unimpregnated wood fl0ur.
5. A molding composition comprising a thermo-setting resin of the urea type carried as an impregnum in finely divided cellulose and incorporated with unimpregnated cellulose carrying an added curing catalyst.
6. A molding composition comprising a thermo-setting resin of the urea-thiourea type carried as an impregnum in finelydivided cellulose and incorporated with unimpregna'ted cellulose carrying an added curing catalyst.
7. A molding composition comprising a' nated wood flour carrying an added curing catalyst.
9. A molding composition com rising wood flour impregnated with a urea ormaldehyde condensation production admixed with wood flour substantially free from said condensation product, the mixture being capable on subjection to heat and pressure of coalescing to a coherent mass.
10. A molding composition comprising wood flour impregnated with a urea formaldehyde condensation product admixed with dry unimpregnated w od. flour adequate to absorb water of reaction on subjection of the composition to heat and pressure.
11'. A molding composition containing a urea-aldehyde condensation product and a latent catalyst. Y
12. A molding composition containing a urea-aldehyde condensationproduct, a cellulosic filler, and a latent catalyst.
13. A molding composition containing a urea-aldehyde non-acid condensation prod not, and a latent acid catalyst.
14. A molding composition containing a urea-aldehyde non-acid condensation product, a cellulosic filler, and a latent acid catalyst.
Y CABLETON ELLIS.
US1905999A 1930-02-10 1930-02-10 Catalyzed urea resin Expired - Lifetime US1905999A (en)
US1905999A US1905999A (en) 1930-02-10 1930-02-10 Catalyzed urea resin
US1905999A true US1905999A (en) 1933-04-25
ID=23694863
US1905999A Expired - Lifetime US1905999A (en) 1930-02-10 1930-02-10 Catalyzed urea resin
US (1) US1905999A (en)
US2416151A (en) * 1942-12-21 1947-02-18 Courtaulds Ltd Production of cellulosic materials with improved crease-resisting properties
US2418497A (en) * 1944-03-01 1947-04-08 Du Pont Nu-(acylthiomethyl) carbonylamides and their production
US2424284A (en) * 1943-02-22 1947-07-22 British Celanese Fixation of finely divided substances
US2471497A (en) * 1942-06-27 1949-05-31 Celanese Corp Bonding cellulose surfaces
US2482895A (en) * 1946-03-29 1949-09-27 Bemis Bro Bag Co Method of making paper yarn
US2604578A (en) * 1948-01-16 1952-07-22 Hoover Co Detachable light housing for suction cleaner
US2607696A (en) * 1948-01-28 1952-08-19 American Viscose Corp Process of forming a food package
US2871152A (en) * 1955-12-06 1959-01-27 Frank J Tobin Laminated tile
US2931750A (en) * 1954-08-30 1960-04-05 Whirlpool Co Method of making a molded overlay panel structure of low moisture absorption
US3093608A (en) * 1958-10-17 1963-06-11 British Industrial Plastics Molding composition comprising aminoplast resin and cyclic sulphite and method of preparing same
US3174940A (en) * 1961-02-17 1965-03-23 Rhoads Molded Products Inc Process of preparing a molded article from a thermosetting formaldehyde resin and sawdust
US5773494A (en) * 1995-03-14 1998-06-30 Finvimar International B.V. Laser-markable article and a composition containing a urea thermosetting resin for making the same
US2067012A (en) 1937-01-05 Composite building material
US3131116A (en) 1964-04-28 Post forming of decorative laminates
US3275605A (en) 1966-09-27 Amine-modified urea-formaldehyde resins and process of manufacture thereof
US2759837A (en) 1956-08-21 Process of forming molded cellulose products
US3816232A (en) 1974-06-11 Decorated molded article and method of producing it
US2748046A (en) 1956-05-29 Method of edge-surfacing woody products
US3067077A (en) 1962-12-04 Decorative overlay sheets and articles containing same prepared from modified thermosetting melamine-formal-dehyde resinous compositions
US3018206A (en) 1962-01-23 Fire-resistant decorated composite laminate members and method of producing same
US2233875A (en) 1941-03-04 Laminated board and method of making same
US2197724A (en) 1940-04-16 Resinous molding composition from synthetic aldehyde resins and hydrolyzed ligno-cellulose