US2798833A

US2798833A - Sheet metal composition material

Info

Publication number: US2798833A
Application number: US412662A
Authority: US
Inventors: Lapsensohn Lewis; Lapsensohn Richard; Lapsensohn Jacob
Original assignee: Individual
Current assignee: Individual
Priority date: 1954-02-25
Filing date: 1954-02-25
Publication date: 1957-07-09
Anticipated expiration: 1974-07-09

Description

States 2,798,833 Patented July 9, 1957 SHEET METAL CGMPOSITION MATERIAL Lewis Lapsensohu, Erooidyn, Richard Lapsensolm, Glen Oaks, and Jacob Lapsensohn, Brooklyn, N. 51.; said Richard Lapsensohn and said Jacob Lapsensnhn assignors to said Lewis Lapsensolm No Drawing. Appiication February 25, 1954, Serial No. 412,662

6 Qlaims. (Cl. l54---45.9)

This invention relates to an improved article of manufacture, and particularly to an improved sheet metal composition adaptable as a roofing and flashing material.

Composition materials for roofings and flashings have been known and used for many years. The very first material of this type to appear on the market consisted of a metallic sheet or veneer to which was applied an asphalt-coated felt. The metal veneer was applied while hot so as to cause it to adhere more securely to the coated felt. The material did not receive a wide commercial acceptance because the asphalt layer in contact with the metal cracked and was readily broken loose by sudden shock. From the manufacturing point of View, it had the disadvantage in that the metallic sheet or veneer had to be heated and pressed firmly to the asphalt-coated felt. Realizing the shortcoming of this material, the roofing industry experimented with various bituminous mastic compositions which would serve as a binder or adhesive and which would be nonflowing, non-cracking, and practically non-water absorptive. The bituminous mastic was obtained by heating a mixture of heavy water-gas-tar and powdered bituminous coal in a still at a temperature ranging between 300 and 350 C. for a period of time of about /2 hours. The temperature was maintained for several hours, the heating discontinued and the mixture allowed to cool. Within one hour after the temperature slowly dropped, additional water-gas-tar-heavy oil was stirred into the heat-treated coal and tar mass. The resulting product was discharged from the still and constituted the binding material. To the latter, sand, clay, fibers, either mineral or vegetable, i. e. asbestos cotton, hair, etc. were added. As an alternative, the fibrous material was precoated with the binding material, or other pitch tar, or high boiling tar distillate. The resulting mastic containing coal-digestion pitch was directly bonded to the metal surface by heat and pressure. The bituminous mastic coated metal sheet did not prove successful because of certain disadvantages. The first was that when the coated metal sheet was exposed to the suns rays, especially during the hot summer months, the mastic became loose and detached itself from the supporting metal sheet. In other words, materials of this type were unable to withstand the heat of the sun especially when utilized roofing materials or flashings.

To overcome the shortcomings of the bituminous mastic coated metal sheet, the industry conducted further experiments with the thought of decreasing or eliminating the detachability of the mastic material from the metal sheet. To achieve this objective it was thought that if to an asphalt mastic composition, containing a bulk-forming filler, a sufiicient quantity of lime were added and the mixture heated, the lime would interact with the moisture and asphalt and cause the surface portion in contact with the metal to harden. In other words, if the mixture containing the lime were applied to a sheet metal and heated, the heating process in presence of the lime would render the asphalt inert so that subsequent reheating to the same temperature would render the asphalt non-fluid and thereby avoid detachment or release of the mastic layer from the metal sheet. This expedient did not prove commercially practicable because of the heat-treatment involved. In addition, when exposed to the hot sun-rays of the summer months, the asphaltic mastic composition still detached itself from the supporting sheet metal because of the fluidization of the asphalt material.

To overcome the above shortcoming, attempts were made to flex or crinkle the sheet metal coated material after the heating treatment. This, however, did not prove practical due to the fact that metal foils have a different coefiicient of expansion from that of the asphalt coating base, hence when such material was exposed to heat the metal foil became ruptured, loosened or detached from the asphalt base.

Another method used was to subject a metal foil coated with an asphalt base over which was applied an asphalted felt to a set of rollers which would form wrinkles or ridges followed by longitudinal flexing of the foil coated base to form transverse wrinkles or ridges. This expedient did not solve the problem of preventing the asphaltic coat or adhesive layer from detaching itself from the supporting metal sheet during exposure to the suns rays.

Despite these various attempts to provide an improved product, the building material industry reverted to the manufacture of the composition material of the asphaltcoated type applied to a metal sheet or veneer. This material is still unsatisfactory because of the sludging and separation of the asphaltic layer or adhesive between the asphalted felt and sheet metal or veneer when the asphalted-felt side is applied to a surface previously coated with a cut-back asphalt. It has been found that the lower boiling solvents in the cut-back asphalt penetrate or diffuse quite rapidly through the asphalted felt layer and come in contact with the asphalt layer. As a consequence thereof the layer tends to sludge and gradually separate from the metal sheet or veneer. In other words, the asphaltic layer begins to flow regardless whether the metal sheet or veneer is flat, corrugated, wrinkled or otherwise.

To provide a new sheet metal composition adaptable as a roofing and flashing material comprising a sheet metal or veneer bonded to a layer of a fibrous material free of all of the foregoing objections and shortcomings constitutes the principal object of the present invention.

Another object is to provide such composition in which there is permanent adhesion between the sheet metal or veneer and fibrous material.

A further object is to provide such composition in which the bonding agent is non-flowing, non-cracking and weather resistant.

A still further object is to provide such composition which retains its unitary structure with extreme changes in temperature without rupture or detachment of the sheet metal or veneer from the fibrous material.

Other objects and advantages will become apparent from the following description.

In order to attain all of the foregoing objects, we have found that the bonding or adhesive layer to be employed between the sheet metal or metal veneer and the fibrous material comprises a mixture of a polysulfide polymer and a resinous material selected from the class consisting of epoxy ether resin, polyamide resin, resorcinol formaldehyde resin, cresolor alkylated phenolformaldehyde resin, and related phenolic resin of the A or B stages. Witheither one of these mixtures, after curing, a bond or adhesive layer is obtained which will 35 not flow at elevated temperatures, above 100 C., will not crack at temperatures as low as -65 F. and which has a high degree of flexibility, water and water vapor resistance, and resistance to solvents; especially those utilized in cut-back asphalts.

The mixture of the bonding agent is'applied to one side of the sheet metal or metal veneer by the usually employed coating machines to a thickness ranging from .001 to A.; of an inch. The coating is applied directly while the sheet metal or metal veneer is travelling from a roll along fixed rotating rollers. After the coating layer has been applied, a strip of self-supporting sheet of fibrous material having a thickness of 0.001 to of an inch from an adjacent roll is applied directly to the coated surface and immediately fed between two pressure rollers rotating in the same direction to firmly press the fibrous material to the coating. A short distance away from the two rollers a series of infra-red lamps may be placed so that as the fibrous material and coating come in contact sufficient heat is given off to accelerate the curing of the bonding or adhesive layer. This process is conventional and is operated in a continuous manner. The application of heat is optional, since the curing of the bonding layer takes place after application and within one-half and one and one-half hours.

The sheet metal or metal veneer to be coated may be aluminum, copper, zinc, galvanized sheet metal, stainless steel, Monel metal and the like. In fact the constitution of the sheet metal is immaterial since any commercially available sheet metal can be coated with the bonding agents employed herein. The thickness or gauge of the sheet metal may range from .001 to of an inch.

The fibrous material may be of any type, such as, for example, cotton fabric, canvas, woven asbestos, glass fiber such as roving, matte and the like, rag paper, kraft paper, asbestos paper, cardboard, or any natural or synthetic fabric either alone or laminated with a glass fiber and the like may be used as such or impregnated with asphalt and employed as the foundation base. Instead of these fibrous materials asphalted-felt may be employed.

The asphalted-felt may be any one of the commercially available materials such as 10, 15, 60 or 90 1b. asphaltfelt. Of these, we prefer to use the standard 15 lb. asphalt or coal tar pitch felt.

As an alternative, one surface of the sheet metal may be coated by means of the conventional lithographic roller with any metal, paint, enamel, or commercially available metal surface coating containing synthetic resins such as epoxy ether esters or epoxy ethers modified with a urea-formaldehyde resin or a phenolic resin, and the like. These coatings may contain dispersed copper, bronze, or aluminum powder or inorganic pigments normally used in outside paint and enamel formulations.

The sheet metal or veneer, after receiving the outside coating of paint or enamel, is passed along a roller to a baking oven having an internal temperature of about 300-800 F. and kept there for about ].60 minutes. During this time the coating cures and dries to an insoluble infusible state. It is then Wound on a roller and employed for the coating of the bonding or adhesive layer.

The surface coated sheet metal or metal veneer prepared as above is then directed on rollers to the coating machine for application of the bonding or adhesive agent and fibrous material, after which it is passed through the pressure rollers, and, if desired, passed further through conventional rollers adapted to impress crimps, corrugations, or embossed designing.

The following are the components utilized in preparing the mixtures of the adhesive or bonding agent between the fibrous material and sheet metal or metal veneer:

The polysulfide polymers, which constitute one component of the mixture and which are mixed in the proportion of 25 to 100 parts by Weight per 25 to 100 parts by weight of either polyamidc resin, epoxy ether resin, or any one of the commercially available phenolic resins 4 containing a reactive methylol group, are characterized by the following formula:

wherein m represents a positive integer of from 3 to 23. These polymers are mobile liquids and have a molecular weight ranging from 500 to approximately 4000. They are commercially available under the registered trademark Thiokol liquid polymers. The methods of their preparation are well known to the art and need not be described herein.

Instead of the foregoing polysulfide polymers, we can also employ polyhydroxy polythio polymers disclosed in U. S. P. 2,527,375, and the polythiopolymercaptans having a molecular weight of about 500 to 12,000 which are mobile liquids at 25 C., prepared according to the methods given in United States Patent 2,466,963. The disclosures of both of these patents are incorporated herein by reference, and referred to hereinafter and in the claims as polysulfide polymer.

We have found that 25 to parts by Weight of the above polysulfide polymers, and 25 to 100 parts by weight of a polyamide resin form compatible solutions with chlorobenzene, chloroform, cyclohexanol, methylene chloride or ethylene dichloride or mixtures thereof. When 50 parts by Weight of the polysulfide polymer and 25 parts by weight of polyamide resin are dissolved at room temperature in 100 to parts by weight of the solvent or solvent mixture, a solution suitable for direct coating to the sheet metal, metal veneer or fibrous material is obtained. 3 to 6 parts by weight of any aliphatic or aromatic amine, preferably 2,4,6-tri(dimethylaminomethyl) phenol or diethylene triamine, or dimethylaminopropylamine may be added per 100 parts by weight of the solvent-polymer-resin mixture to accelerate the curing reaction at temperatures varying between 20 and 75 C. Temperatures higher than 75 C. may be employed, if desired, to accelerate the evaporation of the solvent or solvent mixture employed in preparing the coating mixture. The usual fillers such as calcene, aluminum silicate powder, etc. may be added in an amount ranging from 10 to 100 parts by weight per 100 parts by Weight of the prepared polymer-resin-solvent mixture.

The cresolphenoland urea-formaldehyde resins which are mixed with polysulfide polymer may be any one of the phenolic resins that are currently available on the market. As illustrative examples of such phenolic resin, the following may be mentioned:

Phenolic oil soluble BR 3360 Superbeckacite 1001 Urea-formaldehyde resin Beetle 227-8 It is to be noted that the nature or character of the phenolic resin is immaterial so long as it contains a reactive methylol (-CHzOH) group on the phenol ring.

With phenolic resins and polysulfide polymers, the hydrogen is split from the mercaptan (-SH) terminal of the polymer and hydroxyl from the methylol group of the resin to form a monosulfide linkage and water. With epoxy ether resins and polysulfide polymers, the hydrogen from the mercaptan terminal of the polysulfide polymer is split and unites with the epoxide to form a hydroxyl group. With polyamide resin and polysulfide polymer it is believed that an esterification takes place with the splitting out of water.

The polyamide resin which is mixed with the polysulfide polymer is a resinous product obtained by the condensation of a mixture of dimerized and trimerized unsaturated fatty acids of vegetable oils including dibasic and tribasic acids with diethylene, triamine. It is characterized by the general formula:

wherein R represents the aliphatic chain of the unsaturated fatty acids and n represents a numeral ranging from 5 to 15, with an acid number ranging from 7 approximately to 85 approximately. The various grades of these resins, which are available on the market, and the methods of preparing them are Well known to the art and need not be discussed herein. In addition polyamide resins obtained by the condensation of dibasic organic acids such as, malonic, maleic, fumaric, succinic, glutaric, a,m'-oxydiacetic, adipic, pirnelic, phthalic, tetrahydrophthalic, suberic, azelaic, sebacic, etc., with alkylamines such as ethylene diamine, triethylene tetramine and tetramethylene pentamine may also be employed.

The unsaturated fatty acids employed in preparing the dimers and trimers for condensation with ethylene diamine or diethylene triamine are oleic, linolic, linoleic, linolinic, 'y-hexanoic, tetracrylic, etc., or mixtures thereof.

For purposes of the present invention we prefer to employ a polyamide resin having an average molecular weight of 3000-6500, a ball and ring softening point (A. S. T. M.) C. of 28 or 43 minimum, and viscosities (Gardner-Holdt) of A3-D which are determined as a 35% solution of the resin in a 1:1 mixture of butanol and toluene when mixed With a polysulfide polymer. In such mixture the proportions range from 70-75% of polysulfide polymer and 30-25% of polyamide resin.

The foregoing polyamide resins are sold on the market under the brand name designation #1008, #110, #938, #948 and #958, respectively.

The epoxy ether resins, commonly referred to as, polyglycidyl ethers of polyhidric alcohols and glycidyl ethers of bis-phenols, employed in accordance with the present invention, are characterized by the following general' formulae:

wherein R represents the divalent hydrocarbon radical of the dihydric phenol and n represents the extent of copolymerization as determined by the epoxy equivalent which ranges from 140 to 4000. By the epoxy equivalency is meant the average number of 1,2-epoxy groups 0 Q l 1 contained in the average molecule. It is expressed in the trade as the grams of the polymeric material or resin containim one gram equivalent of epoxide.

The epoxy others are obtained by the procedures described in United States Patents 2,500,600; 2,633,458; 2,642,412; 2,324,483; 2,444,333; 2,520,145; 2,521,911; all of Which are incorporated herein by reference for examples of the types of epoxy ether resins that may be employed in admixture with polysulfide polymers.

Of the several types with varying epoxide equivalents, We prefer to employ the epoxy ether resin having an epoxide equivalent ranging between 190-210 and 225-290, preferably the former because of its low melting point, 8-12 C. (as determined by Durrans mercury method) and ease of formulation with other components.

The proportion of epoxy ether resin may vary from 25 to 100 parts by weight per 25 to 100 parts by weight of a polysulfide polymer. To the mixture are added from 1 to 20 parts by Weight of any one of the known aliphatic or aromatic organic amines as disclosed in U. S. P. 2,500,600 and 2,643,412, to cure the components. For direct, i. e. immediate, application to either sheet metal or fibrous material, 100 to 120 parts by Weight of aluminum silicate powder or other filler are added and the mixture stirred. When the temperature of the mixture ranges from 16 to 25 C., 3-6 parts by weight of the amine per parts of epoxy ether resin are added. When the temperature ranges between 25-40 C., 2-3 parts by weight of the amine per 100 parts of epoxy ether resin are added. In the case where a lapse of time takes place, i. e. after mixing and prior to coating-usually about 30 minutes-and the temperature ranges from 20 to 30 C., 3-6 parts by weight of the amine per 100 parts of epoxy ether resin are added to the mixture.

In some instances it is desirable to incorporate into the bonding or adhesive mixture prior to the coating of the sheet metal, metal veneer or fibrous material, a filler. This filler appears to improve the bond between the sheet metal and fibrous base material. Such fillers may be one or a mixture of the following materials:

The following examples will show the preparation of some of the foregoing adhesive or bonding mixtures. It is to be clearly understood that they are merely illustrative and that the invention claimed is not to be limited thereto. All the parts given are by weight.

EXAMPLE I Epoxy ether resin (sold under the brand name of Epon 828 and having an epoxy equivalent of 190-210) 100 Polysulfide polymer (sold under the name of Thiokol LP-33 having a molecular weight of approximately 1000 100 Aluminum silicate powder Diethylaminopropylamine 6 The first two components are thoroughly mixed or blended at room temperature. To this mixture is added with stirring the aluminum silicate powder until a uniform dispersion is obtained. The diethylaminopropylamine is then added and the mixture stirred. again.

An aluminum foil of approximately 1/250 of an inch in thickness and approximately 36 inches wide, which was coiled on a separate roll, was passed on a roller of a conventional coating machine equipped with a doctor roll and the above coating applied from a coating roll to one side of the foil to a thickness of 0.002 to 0.007 of an inch. A 15 lb. asphalt-felt, coiled on a separate roll, was placed in contact with the coated side of the aluminum foil. After contact the felted-metal foil was wound on a single shaft center-rewind. Intimate contact between the felt and coated aluminum is obtained by means of the conventional breaking device providing tension on the roll coil containing the aluminum and on the roll coil containing the asphalted-felt.

Should the temperature during coating exceed 30 C.,. i

say between 30-40" C. a small mount of either toluene or xylol may be added to the coating mixture as a thinner or diluent so as to retard the curing of the bonding or adhesive mixture during the coating operation.

The felted side of approximately 36" square of the metal foil prepared as above was coated evenly with a cut-back asphalt of the type employed by roofers and allowed to remain for a period of 4-8 hours. After that time there was no separation of the asphalted-felt from the adhesive layer or bonding agent. This clearly established that while the volatile solvents from the cutback asphalt penetrated the felt, there was no effect on the bond or adhesive layer between the asphalted felt and metal foil.

The uncoated aluminum side of a strip of approxi- Lmately 6" square of the felted-foil, prepared as above, was exposed to heat 'of approximately 400 C. from a blow torch placed at distance of 12 inches from the foil for a period of 30 minutes. After the foil cooled toroom temperattue, an attempt to pull or peel off the asphalted felt away from the adhesive or bonding layer, failed. The metal foil could be flexed and bent Without loosening or detaching the bonding ar adhesive layer.

The foil prepared as above is of value not only as a roofing material but also as a flashing and reflective insulation in sidewalls, under roof rafters, on ceilings, and beneath the floor in basementless homes. It may be used in place of building paper to protect against rot-promoting moisture within the walls.

It may also be used on the roof of a building as a valley flashing, a vent pipe flange, a chimney flashing and as an under flashing.

EXAMPLE II An aluminum foil of approximately of an inch in thickness and approximately 36 inches wide was coated with the following composition:

Epoxy ether (sold under the brand name of Epon 1007 and having an epoxy equivalent The first two components were cooked at 500-520 F. for about 2 hours and allowed to reach room temperature. The xylene and cobalt naphthenate were then added.

To each gallon of the above cooled formulation, l-3 lbs. of finely powdered metallic copper were added and the mixture stirred until a uniform dispersion was obtained.

The finished coating composition was applied to the aluminum foil by means of lithographer roller and the coated foil passed along rollers to a heated oven, the internal temperature of which was approximately 300- 800 F. and allowed to remain there for about 1-60 minutes. Thereafter, the coated foil was bonded to the fibrous material as in Example I and crimped.

Instead of the above formulation which can be applied as an outside coating to the metallic foil prior to bonding or coating with the adhesive layer, we have found that the mixture of soya bean fatty acids and dehydrated castor oil can be replaced by varying amounts of ureaformaldehyde resins, melamine-formaldehyde resins, or phenol-formaldehyde resins or mixtures thereof. When such replacements are made the volatile solvent thinner may consist of 25 parts by weight of ketones, aromatic hydrocarbons, acetates, alcohols, ether alcohols, ether alcohol acetates, and the like. Compositions of this type readily cure within 1-60 minutes at 300550 F. or higher.

The foil as prepared above is of exceptional value as a flashing material to the building trade. It is recognized that masonry Walls cannot be depended upon to be permanently waterproof, even though the brick, stone, terracotta or other materials may be waterproof as a. unit and the mortar used may be rich enough to be considered waterproof. The shrinkage of these materials and the natural movement of the building may cause a masonry wall to leak. It is, therefore, highly desirable to have the flashing so located as to prevent rain water or moisture that may enter the exterior wall from coming in contact with steel or wood members in the wall, and seeping into the side of the building.

There are several kinds of material that are used as flashing such as asphalt saturated felts, metal sheet bonded to asphalt felt by means of asphalt or asphalt mastics, and sheet metals such as copper, aluminum, zinc, galvanized sheet metal, and the like. Flashing of this type once built into the wall cannot be replaced when worn or corroded without tremendous replacement cost. The sheet metals, particularly aluminum, corrode in time because of the alkaline materials in the mortar, cement, etc.

The composition foil prepared according to Example II avoids the above shortcomings, since the outer coating is extremely resistant to corrosive action and once installed is durable, prevents leaks, and solves drainage and penetration problems.

EXAMPLE III Mixture A Polyamide resin (sold under the brand #1008 and having an average molecular weight of 3000-6500 The resin is dissolved in the mixture of the solvents at room temperature until a clear liquid is obtained.

Mixture B Epoxy ether resin (sold under the brand name of Epon 864 and having an epoxy equivalent to 300-375) 20 Methyl ethyl ketone 10 Toluene 10 The epoxy other is dissolved in the mixture of solvents at room temperature until a clear liquid is obtained. Mixtures A and B are combined with stirring and 6 parts of diethylamin'opropylamine added while stirring was continued. The solution was applied to the aluminum foil and then contacted with a 15 lb. asphalted-felt. The bonded foil was treated as in Example I.

The cure of the adhesive or bonding agent can be expedited by passing the foil through the oven for 2 hours at 60 C. or for 5 to 15 minutes at C.

When the felted side of the bonded foil was coated with the cut-back asphalt, the same results as in Example I were obtained. The heating of the uncoated side of the aluminum, as in Example I, showed no cracking, no flowing and no detaching of the adhesive layer from either the metal and felt surfaces. The adhesive or bonding layer was elastic and as a consequence the foil could be flexed and bent.

EXAMPLE IV Example I was repeated with the exception that the adhesive or bonding mixture was replaced by the following:

The liquid phenolic thermosetting resin was mixed with the polysulfiide polymer and 14 parts by weight of 2,4,6-tridimethylaminomethyl) phenol added and the mixture applied as a coating. Instead of the above liquid phenolic thermosetting resin, we can also employ liquid phenolic resins available under the brand names of BL3128, BZ9700, XV 17656, Plyophen 5010, etc. All of these phenolics contain a methylol group and as a consequence reactive with the other components of the adhesive or bonding mixture.

EXAMPLE V Example I was repeated with the exception that the aluminum foil and 15 lb. asphalted-felt were replaced by an aluminum foil of 0.008 in thickness and woven asbestos fabric having a thickness of about 4 of an inch.

EXAMPLE VI Example I was again repeated with the exception that the asphalted-felt was replaced by kraft paper having a thickness of A of an inch. In this coating application, it was found that the adhesive or bonding agent did not completely saturate the paper and that a definite film of the bonding agent can be observed between the kraft paper and sheet metal.

The only precaution to be observed in the practice of this invention is that when outer coating such as in Example II is to be applied to the sheet metal or metal veneer, it is desirable that such coating be applied first, followed by the application of the adhesive or bonding agent to a fibrous material. The reason for this is that since the outside coating must be heated while in the oven to accelerate the curing of the coating composition, there is likelihood that the fibrous material, such as paper, cardboard, fabric, felt, canvas, and the like, may be adversely affected.

As may be noted from the foregoing description it is immaterial whether the sheet metal or the fibrous material are coated with the adhesive or bonding agents employed in accordance with the present invention, the choice being left to the discretion of the operator of the coating machine.

Instead of employing the polyamides obtained by con- (lensing a mixture of dimerized and trimerized unsaturated fatty acids including dibasic and tribasic acids with diethylene triamine, polyamides, obtained by the condensation of dimerized and trimerized unsaturated fatty acids with ethylenediamine may also be used. Such polymers are characterized by the general formula:

wherein R represents the aliphatic chain of the unsaturated fatty acids and n represents a numeral ranging from 5 to 15, with molecular weights of 3000 to 9000. Various grades of these resins are available on the market, and the methods of preparing them are well known to the art and need not be repeated herein.

We may also employ a mixture of two polyamide resins of different viscosities and of different average molecular weight. In such case, a mixture consisting of -40% of a polyamide resin having a viscosity of C maximum (Gardner-Holdt); 30-20% of a polyamide resin having a viscosity of B-D (Gardner-Holdt) and an average molecular weight of 6000-9000; 30-20% of a polyamide resin having a viscosity of A, C (Gardner-Holclt) and an average molecular weight of 3000-6500, and 30-20% of a polyamide resin having a viscosity of A3-Al (Gardner- Holdt) and an average molecular weight of 3000-6500 per 100 parts of such mixture, 10-20 parts of plasticizer, such as tricresol phosphate and the like, may be added to impart flexibility to the resin mixture after curing. Instead of plasticizers one part by weight of a saturated solution 10 of a synthetic or natural rubber may be incorporated per one part by weight of the mixed polyamide resin. To such mixtures from 1-15 parts by weight of any of the aforementioned aliphatic organic amines may be employed as curing agent.

The mixture of polyamide resins of different viscosities may be dissolved together in a 1:1 mixture of isopropanol and toluene, mixtures containing 30, 50 or 70% of toluene and 70, 50 or 30% of isopropanol may also be employed.

We have also found that by replacing the polysulfide polymer of the epoxy ether resin mixture by an equivalent amount of a solution of natural or synthetic rubber, chlorinated rubber, depolymerized rubber, neoprene, butadiene-acrylonitrile copolymer, butadiene-styrene copolymer and the like. Such rubber solutions, in. appropriate solvents normally used to dissolve such rubbers, may be employed in lieu of the polysulfide polymers in all of the foregoing adhesive or bonding mixture compositions.

It is to be clearly understood that by the term polysulfide polymer as employed in the appended claims, we include the polysulfide polymers characterized by the general formula and having molecular weights ranging from 500 to approximately 4000, the polyhydroxy polythio polymers disclosed in U. S. P. 2,527,375, and the polythiopolymercaptans having a molecular weight of about 5,000-12,000. Similarly, by the term phenolic resin we include only the phenolic resins or phenolic condensation products disclosed herein and their obvious equivalents.

While we have herein disclosed the preferred embodiments of our invention, we do not thereby desire or intend to limit ourselves solely to the foreging specific examples, since it will be readily apparent to those skilled in the art that the precise proportions of the materials r utilized in the preparation of the adhesive or bonding composition may be varied and other materials having equivalent chemical or physical properties may be employed, if desired, within the spirit and scope thereof, and therefore, such limitations should be imposed as they are indicated in the appended claims.

We claim:

1. A laminated article of manufacture comprising a self-supporting sheet of asphalt-impregnated. fibrous material and a metallic sheet adhered thereto by a mixture of a bonding agent comprising 25 to parts by weight of a polysulfide polymer which is a mobile liquid at 25 C., having a molecular Weight of 500 to 12,000 and having the following structure:

wherein m represents a positive integer of from 3 to 23, 25 to 100 parts by weight of a glycidyl polyether of a polyhydric phenol having an epoxy equivalent of from to 4000.

2. A laminated article of manufatcure according to claim 1 wherein the polysulfide polymer has a molecular weight of approximately 1000.

3. A laminated article of manufacture according to claim 1 but wherein the glycidyl polyether of a polyhydric phenol has an epoxy equivalent of -210.

4. A laminated article of manufacture according to claim 1 but wherein the metallic sheet is aluminum.

5. A laminated article of manufacture according to claim 1 but wherein the fibrous material is 15 lb. asphalt felt.

6. A laminated article of manufacture according to claim 1 but wherein the metallic sheet adhered to the sheet of fibrous material is crimped.

References Cited in the file of this patent UNITED STATES PATENTS 1,996,951 Clark et al. Apr. 9, 1935 (Other references on following page) 11 12 UNITED STATES PATENTS 7 Technical Service Bulletin #103, pamphlet by Thiokol 2,466,963 Patrick et a1 Apt 12,1949 P- n New y, of June 9 p g s 14, 2,469,141 Alexander May 3, 1949 Thlollol 2 618 Watkins 25 1952 Thlokol L1qu1d Polymer LP2, pamphlet by Thlokol 5 Corp., Trenton, New Jersey, of Febuary 24, 1948, pages OTHER REFERENCES 15 and 7 Polysulfide Liquid Polymers, article by J. S. Iorczak et al., reprint from Ind. & Eng. Chem, vol. 43, page 324-328, February 1951.

Claims

1.A LAMINATED ARTICLE OF MANUFACTURE COMPRISING A SELF-SUPPORTING SHEET OF ASPHALT-IMPREGNATED FIBROUS MATERIAL AND A METALLIC SHEET ADHERED THERETO BY A MIXTURE OF A BONDING AGENT COMPRISING 25 TO 100 PARTS BY WEIGHT OF A POLYSULFIDE POLYMER WHICH IS A MOBILE LIQUID AT 25* C., HAVING A MOLECULAR WEIGHT OF 500 TO 12,000 AND HAVING THE FOLLOWING STRUCTURE: