KR860000460B1 - Composites and methods for providing metal clad articles and articles produced thereby - Google Patents

Abstract

A composite for providing a metal clad articles of thermosetting resin includes a metal facing, a curable thermosetting resin, and a layer of adhesive between the metal facing and the resin.The adhesive sticks both to the metal facing and to the thermosetting resin on curing of the resin, thus bonding the metal with the resin. The thermosetting resin may be cured hot or cold.

Description

Composite materials for the production of metal laminates, metal laminate products using the same and a method of manufacturing the same.

The present invention relates to a synthetic agent for producing a metal laminate product of a heat curable resin, a method for producing the metal laminate product, and a metal laminate product produced according to the method. Fiber-reinforced plastic (FRP) foils, in particular fiber-reinforced plastic laminates based on heat curable resins such as unsaturated polyesters, vinyl esters, epoxides, phenols, furans and silicones, are widely used in the industry.

With the correct choice of resin type and reinforcement, these sheets are used for pipes, conduits, tanks, containers in chemical plants, laminates and decorative panels for buildings, containers for beverage liquids and foodstuffs, tanks and pipes, boats and automobiles. And the manufacture of commercial transport, trains, and a variety of other applications.

However, there are some aggressive environments that can erode some or all of the resin matrix being used.

This disadvantage has been overcome to some extent by the use of thermoplastics such as polyvinyl chloride (P.V.C) polypropylene or fluorinated ethylene / propylene interpolymers in the finishing of sheet metals.

Even so, metals such as aluminum and stainless steel are used more than FRP or FRP with thermoplastic surfaces, except where the brightness and load-bearing properties of FRP are advantageous.

It is now expected that very thin metal sheets (eg stainless steel), only about 0.008 cm thick, will be available, and this type of material, followed by FRP, may be used for example, building decoration phenyls on metals, section water tanks on metals, It may be used in dashed metal pipes, conduits and tanks, and metal parts for the transportation industry. Unfortunately, no matter how carefully prepared the surface of the stainless steel, little adhesion occurs between the stainless steel and the heat curable resin, i.e. standard unsaturated polyester and vinyl ester.

Some resins, such as epoxides and polyurethanes, are known to adhere automatically to stainless steel (British patent 2,061,834) but are disadvantageous for use due to other disadvantages such as cost (epoxide) and low strength (polyurethane).

The inventors of the present application have found a way to allow good adhesion between certain metals and heat curable resins which are generally not considered to be adhesive to metals.

In accordance with the present invention there is provided a synthetic agent for the manufacture of a metal laminate, the composite being a metal surface, a heat curable resin capable of curing, and between the metal surface and the resin, but also adhering to the metal surface and heat curable It consists of a layer of adhesive material that can also adhere to the resin, which together form an adhesive bond while curing of the aforementioned resins takes place.

While this composite material is cured, a metal laminate according to the invention is provided, wherein the metal surface is efficiently and easily bonded with the heat curable resin by means of an adhesive.

The method of the present invention provides a layer of adhesive material that can adhere to the metal surface on a metal surface, by placing a curable heat curable resin on the layer of the adhesive material and then curing the heat curable resin. This adhesive material is combined with a resin to produce the above-mentioned metal laminate.

In order to form a metal having the desired appearance, it is carried out before the combination of metal and other materials takes place.

The process of the invention can be used in particular for the production of metal laminate sheets of fiber reinforced heat curable resins.

The method of the present invention is valuable in that one thin plate is formed on the metal surface rather than the adhesion between the metal surface and the preformed thin plate. Therefore, the coating of the metal occurs at the same time that the heat curable resin meets the adhesive material and the metal to prepare and cure the thin plate. That is, curing occurs to provide a surprisingly good adhesive bond between the metal and the layer of the resin, resulting in bonding of the layer of adhesive material and the heat curable resin.

To ensure good adhesion between the metal and the heat-curable resin, the metal surface is treated with one adhesive material selected from various primers or adhesives (the choice of adhesive material will be discussed in more detail later). It is good to dry or harden this, but you may use together a heat-purifying resin and a reinforcing material (if desired) in the uncured state, and then harden a heat-curable resin. Heat curable resins (if desired) can be cold-formed, elastic bag (BAG) molded, rotary molded under standard processes in the wet state, such as hand-fitting, spraying, filament winding, resin injection, vacuum assist or without hollow assist. Used in combination with reinforcements by pultrusion or the like, which can be cured at ambient or high temperatures, or can be pre-impregnated or prepared molding materials, eg sheet molding compounds (SMC or its "high-performance" derivatives) , XMC), Bulk, Molding Compound (BMC), Dough Molding Compound (DMC), Fine Particles, etc. may be contacted with a pretreated surface, compressed and then cured by heating under conventional thermocompression molding conditions. .

The metals can be shaped by compression, cutting, welding, warping, trapping or the like before lamination.

When reinforcing the heat curable resin, natural fibers such as jute and reinforcing fibers of, for example, glassy, silica, carbon, KEVLAR ^R and similar polyamides may be used.

At least one layer of the reinforcing fibers is made of fibres, which may be better if the heat-curable resin has been impregnated beforehand (“prepreg”). However, these fibers may be degraded in a heat curable resin as in the case of DMC.

Available adhesives were classified according to their general chemical properties. (Adhesives Directory 1981, Wheatland Journals Ltd, Rickmansworth):

(a) natural products, eg starch bone,

(b) celluloses (materials containing fibrin as the main component), eg Acetate cellulose,

(c) elastomers (rubber-like materials), eg natural rubber.

, 스티렌/부타디엔,(b) synthetic rubber, eg. Nitrile, neoprene

, Styrene / butadiene,

(e) thermoplastic resins, eg. Cyanoacrylates, high temperature soluble materials (e.g. ethylene / vinyl acetate, polyamides, polyvinylbutyral, acrylics and interpolymers,

(f) flammable curable resins, eg. Addition polymers such as epoxides, polyesters, vinyl esters, urethanes, acrylates, urethanes, oxygen-free acrylics or condensation polymers, such as phenol formaldehyde, urea formaldehyde,

(g) minerals, eg. Sodium silicate.

It is generally known that the adhesives in (a), (b) and (g) are not used. In particular, the inorganic adhesives (g) tend to be so hard that they do not bond well with the heat curable resin forming the sheet.

Preferred adhesive materials are selected from several of (f) and (c), (d) and (e) which are included in the latter group in emulsion form, namely (c), (d) and (e). Aqueous adhesives are not known to be very good.

However, these aqueous adhesives also provide adequate adhesion during curing of the heat curable resins that form the sheet at high temperatures.

The adhesive ability of the adhesive material is evaluated to be good if the resulting lap shear of the resulting metal plywood is at least 3 Megapascals (MPa), preferably at least 3.5 Megapascavls.

Lap shear strength should be at least 2.5 MPa.

The choice of adhesive material is the nature of the heat curable resin to form the sheet (the adhesive material and the resin should be compatible). And the metal surface provided and also depends on the curing conditions to be used.

Some adhesive materials can only be used with thin sheets that are cured at high temperatures, which can lead to good results, including some thermoplastics, natural rubbers and synthetic rubbers.

Such high temperature curing is generally carried out under pressure (about 1000-2000 psi, preferably 1500 psi) at 100-200 degrees Celsius, preferably 140-160 degrees Celsius, more preferably 150 degrees Celsius.

On the other hand, other adhesive materials may be used with either a thin sheet that is cured at internal temperature or a thin sheet that is cured at high temperatures. These adhesive materials include some heat curable resins and synthetic rubbers.

Such cold curing is generally carried out under ambient temperature but then a "post-cure" step may also be carried out in which the material is heated to 30-120 degrees Celsius, preferably at least 40 degrees Celsius.

To achieve good results, whether hot or cold or thin, the adhesive is chosen to:

(a) to provide an advantage to the metal surface (there are several adhesives known to be useful for bonding metals with metals, some of which are useful in the process of the invention, if not all).

(b) flexible, tough or elastic, ie low elasticity, and

(c) Can be cured to a minimum shrinkage rate by crosslinking before use of the thinning resin.

Examples of adhesives that produce good results are heat curable resins, acrylic resins that contain polyurethane bonds (although in some cases high temperature curing of the sheet is required) and additionally contain acrylic (particularly acrylate) bonds or end groups. (Especially oxygen-free acrylics), epoxy resins, unsaturated polyesters (if capable of forming a sufficiently flexible layer during curing), and polymers and cyanos containing vinyl acetate residues, nitrile rubbers, polyolefins and high temperature soluble nitrile adhesive residues Acrylates, neoprene, natural rubber, and the like.

Such adhesive materials that provide good results when the thin plates are cured at high temperatures include polymers, ie, high temperature degradable polyolefins containing vinyl acetate residues.

Epoxy resins are more preferred at high temperature curing, but also provide excellent results when cold-curing any heat curable resin that forms a thin plate, that is, epoxy heat curable resin.

Some adhesive materials, such as cyanoalkylates, provide good results for cold and hot cure of thin sheets, but not for hot cure.

In general, adhesives that provide good results, whether cold or hot hardened, can contain acrylics (especially oxygen-free acrylics), unsaturated polyesters as described later, and polyurethane bonds. And heat-curable resins containing acrylic (particularly acrylate) bonds and end groups, and nitrile rubbers.

Nitrile rubber in particular provides excellent adhesion when used together with thin sheets cured at cold and cold temperatures.

These types of adhesives offer a wide range of choices, especially for metals, heat curable resins, and curing conditions, which is surprisingly versatile. Nitrile rubbers, for example, are known as adhesives but in general they have only been applied by high temperature curing in conventional bonding processes. This is in contrast to the good results obtained in cold curing.

Good results can be obtained with cold curing, especially with the adhesives mentioned above.

This allows the process to be carried out without applying heat, thus saving energy and making the process easier and more economical.

In addition, particularly good results can be obtained by allowing the adhesive to fully cure before placing the heat curable resin on the adhesive.

This is especially true when resins curable at cold temperatures, ie epoxy resins, acrylics, nitrile rubbers and urethanes.

Particularly preferred adhesives are those which contain a polyufetane bond with terminal acrylate groups.

A typical method for producing urethane / acrylates of this type is described next.

1.0 M sorbitan and 18.0 M ε-caprolactone were charged into a suitable reaction vessel and heated to 90-100 degrees Celsius with stirring. A cloudy homogeneous dispersion was obtained, to which 0.2% P-toluene sulfonic acid was added. Almost instantaneously it started an exothermic reaction and the temperature rose to 140-150 degrees Celsius. The batch was naturally cooled for 15 minutes and then vacuum dried to remove less than 2% of the charge weight.

After removal the temperature was fixed at 100-110 degrees Celsius and 3.5M isophorone di-isocyanate was added. The exotherm started slowly and the batch temperature rose to 120-130 degrees Celsius, which was suppressed by cooling.

At the end of the exothermic reaction, the batch was cooled to 90-95 degrees Celsius and 3.5 M 2-hydroxy ethyl acrylate and 100 ppm hydroquinone were added. When it began to supply air below the surface, the temperature was fixed at 80-85 degrees Celsius. This batch was kept at this temperature until the isocyanate content was less than 0.6% (equivalent to 95% conversion). The batch was then dissolved in styrene to produce a composition containing approximately 60% solids by weight.

The most useful treatments are known to be based on anoxic acrylics, urethanes, urethanes / acryls and nitrile rubbers, but any other treatment may be used if the three conditions mentioned above are met. For example, standard unsaturated polyesters do not provide any adhesion as they are too hard and exhibit too much shrinkage during curing. However, good bonds can be achieved by using specially prepared unsaturated polyters having a maximum elongation of 50% (in cured form) and a shrinkage lower than normal.

Epoxy materials are also well known metal adhesives, and if they are not well cured prior to the use of heat curable resins that form sheets (with resins other than epoxides), they may attack solvents against partially cured epoxy. Materials filtered from these or partially cured epoxies cause interfacial problems such as impeding the hardening of the FRP.

The adhesive material is used in any suitable form, for example dissolved in a solvent as one melt, or as a powder, or as a separate sheet material. It may be a single component or two components.

Depending on the type of adhesive selected, the adhesive may be applied to the metal surface or simply applied to the metal surface by brushing or spraying.

Some adhesive materials are oxygen-free, that is, they cure properly only in the absence of air, so some thin PTFE sheet is placed on the coating material and left in place until the adhesive layer has cured and then removed before lamination.

Another method is to use adhesives for metals, although this is not particularly desirable. A reinforcement such as a glass chopped strand mat is applied to the metal surface before the binder is cured so that some of the fiber remains in the adhesive layer while most of the fiber protrudes.

Some adhesive materials are hot soluble films that can be dissolved on a metal before the subsequent thinning process or when the entire structure lying between the metal and the molding component, or the metal and the first impregnated material, is cured by high temperature pressurization. Available.

Examples of heat curable resins used to make thin plates include unsaturated polyesters, vinyl esters, urethanes, acrylates, epoxides, phenolic resins, butanes or silicones and are interpolymers, ie urethane / acrylics Rate is also good. More preferred resins are unsaturated polyesters, phenolic resins, futane resins and epoxy resins, which are thixotropic agents (eg gas silica), additives (eg natural calcium carbonate and precipitated calcium carbonate, Clay, live, mica, silica, hydraulic cement) and, if desired, mixed with pigments.

If the resins are polyesters, vinyl esters, and urethane acrylates, these thinnings can be cured by using organic peroxides and heat, organic peroxides and so-called accelerators, visible or ultraviolet light, electron beams, etc. If the resin is an epoxide, it is hardened by a well-known hardener, and when it is furan and phenolic, it is hardened by various catalysts.

The thickness of the metal that can be used in the process is 0.1mm or more, which is wide but usually the thinnest material is used for economic reasons.

Metals used include stainless steel, chromium, titanium, aluminum, tin, copper, lead, zinc, phosphor, bronze, nickel molybdenum, galvanized steel, brass and mild steel. As can be seen by measuring the lap shear and peel strength, debonding the metal with a solvent while adding the adhesive material provides a good bond, but by wiping with a solvent or corrosion with alkali or acid Increased adhesion can be obtained by the abrasion that takes place.

Particularly preferred metal clad laminates of the present invention are metal laminate FRP sheets. Their organization combines the best properties of metals and FRP.

(i) high strength relative to the weight ratio of FRP, which provides components with less weight than when made entirely of metal;

(ii) impermeability of metals where moisture and other aggressive surroundings corrode the FRP and lose its strength and swell after a long period of time;

(iii) chemical resistance of metals, such as stainless steel, titanium, and nickel alloys, in which there are several choices of metals depending on the environment;

(iv) desirable hygiene of metals such as stainless steel which can be used in contact with foodstuffs and beverages,

(v) very good reverse impact resistance, even at high loads, which can be supported without damaging the metal surface;

(vi) fire resistance and nonflammability of metal surfaces critically used in conduits;

(vii) the electrical properties of metals such as electrical conductivity and shielding,

(viii) decorativeness of metals used in panels of buildings and the like.

The metal laminate sheets of the present invention are thus very consumer-friendly, in particular in terms of application of the structure, for example pipes, conduits, ranks, containers of chemical plants, laminates and decorative panels of buildings, It is used in the manufacture of container tanks and pipes for beverage liquids and foodstuffs, boats, automobiles and commercial transport engines, trains and many others, so the range of applications is very wide.

There is no reason why a metal plywood sheet must have only one metal face and both sides may be metal, but the two metals need not necessarily be similar metals.

In a similar manner, a sandwich structure with a light core may be formed, such as a metal foil of one or two sides, for example metal / probe / FRP / foam or honeycomb / FRP, or metal / promoter / Has FRP foam or honeycomb / FRP primer / metal

The thin plate for metal plywood incorporating the present invention, a composite material for producing the same, and a method for forming the thin metal plywood will be described in more detail with reference to the following examples including several comparative examples.

The most preferable specific example of recent years is cold-hardening a thin plate.

Example I

A thin sheet of stainless steel (0.25 mm thick) was degreased with a solvent, and the PERMABOND F241 adhesive (one component of 2 pot acrylic) and Permabond Initiator No. It was coated at 200 m 2 with 1 (curing agent). The layer was covered with polytettafluoroethylene (PTFE) sheet until cured and the sheet was peeled off when cured.

The glass fibers were then quenched with a suitable catalyzed polyester sheet and accelerated by CRYSTIC 272 (unsaturated polyester resin based on isophthalic acid) and a four-layered glass with a ratio of resin to glass of 2.3: 1. The chopped strand mat (450 g / m 2) was used to place on the treated metal surface.

The resulting polyester of synthetic material was cured at ambient temperature to form a metal laminate sheet.

When the polyester cured, it was extremely difficult to separate the cross section of the stainless steel (lap shear strength 3.5 MPa).

Example I A

The sheet of Permabond F241 adhesive made of stainless steel was coated and a piece of silk fiberglass fabric (340 g / m2) was used as Permabond Initiator No. It was immersed in the acetone solution of 1 (9 parts of acetone by weight ratio: 1 part of initiator), and the acetone was evaporated. Rolling this glass fiber onto the surface of the previously treated stainless steel yielded good adhesion.

The glass fiber sheet was then properly catalyzed and the accelerated Crystic 272 and an inner layer of glass with a resin ratio of 2.3: "1 were placed on a glass fabric using finely chopped strand mat (450 g / m2). Let go.

The resulting GRP layer of the composite was cured at ambient temperature, after which it was extremely difficult to separate the stainless steel cross section from the composite.

Example II-XX

Follow the method of Example I but use the treatment set forth in Table I.

TABLE I

Example X XI

A stainless steel 0.25 mm thick sheet was cut to form a flat plate mold of 100 x 260 mm. The metal sheet was solvent degreased and coated with INDASOL MS 419 NF (nitrile rubber adhesive) at 200 g / m 2 and dried. The untreated side of the treated metal was placed in the mold so as to contact the lower mold surface and the mold was filled with RYSTIC M125 (sheet molding compound) and reinforcing fibers to cover 70% of the surface area.

The mold was sealed and the resultant composite was pressed for 4 minutes under a pressure of 150 ° C. and 1500 p.s.i. to give a hardening effect.

The mold was opened to obtain a stainless steel FRP sheet, which had excellent adhesion between the FRP and the metal surface and was very strong (single lap shear strength of 5.5 MPa).

Example XXII-XXXVI

The method of Example XXI was still performed using the treatment set forth in Table II.

TABLE II

Example XXXIIIA

The procedure of Example XXXIII was followed but using Crystic M 225 Sheet Modeling Compound (Refractory).

The impact test shows that the GRP sheet could break without having to penetrate the stainless steel cross section, and there was good adhesion between the FRP and the metal surface (single lap shear strength of 3.5 MPa).

Moreover, after hardening took place, the sheet was easily raised from the mold. The mold walls were made of chromium-plated steel, so the sheets did not stick to the mold walls.

Example XXXVIII-L

The same method as for Example I-XX or XXI-XXXVII was used, but a thin sheet of other metal was used instead of stainless steel.

Example LI

Sheets of stainless steel (thickness 0.5 mm) were solvent degreased and coated with 200 g / m ² INDASOL MS 419 NF (nitrile rubber adhesive). After drying this, the glass-reinforced phenolic resin thin plate was placed on the pretreated side using a four-layer finely torn strand mat (450 g / m 2) having a resin to glass ratio of 3: 1. It was difficult to separate the stainless steel after curing the glass-reinforced phenolic resin thus formed at ambient temperature, and the single lap shear strength of this bond was 3 MPa.

Example LII

The same procedure as in Example LI was performed, but QUAKER furan resin was used as the thinning resin.

Example LIII

The aluminum sheet (thickness 0.5 mm) was degreased with solvent and treated with PERMABOND E 04- (2 pots of epoxy) at 200 g / m 2.

After curing this, a glass-reinforced epoxide sheet was placed on the pretreated side using a four layer finely torn strand mat (450 g / m 2) Epikote 828 + Epicure with a resin to glass ratio of 3: 1.

It was extremely difficult to separate this metal after curing the glass-reinforced epoxide sheet thus formed at ambient temperature. (Wrap shear strength 6 MPa).

EXAMPLE LIV-LVII

The aluminum sheet (0.25 mm thick) was degreased with solvent and treated with INDASOL MS (nitrile rubber adhesive) at 200 g / m 2.

After it was dried, Crystic272 with a resin to glass ratio of 2.5: 1 and one layer of CSM (450 g / m 2) were placed on the treated side.

A 12.7 mm thick PVC foam sheet is pressed into a wet resin layer and a two-layer CSM (450 g / m²) -Crystic 272 sheet is placed on the surface of the foam to form a composite that is at ambient temperature. Curing gave a rigid metal laminate laminate structure in which the foam had cured.

This process was repeated, with alternative foam materials using polyester foams, phenolic foams and polyurethanes.

Example LVII

Section tank shells on metal can be easily manufactured using advanced techniques.

Four corners were cut by 2 inches by 2 inches square from a thin stainless steel sheet 0.5 mm thick and 4 feet 4 inches square and folded to form a flange around a tray of 4 feet by 4 feet.

Edges were joined using welding or soldering. The inner side of the formed tray was degreased with a solvent and then treated with nitrile rubber adhesive at 200 g / m 2 and then dried.

When you send a shaped and ready metal tray to the press's arm tool, the tray becomes virtually part of the tool.

The molds were sealed after filling with a sheet molding compound (SMC) (Crgstic M125) sufficient to obtain a thin plate having the desired thickness.

A stainless steel laminate FRP section tank panel was obtained by flowing and hardening the SMC of the composite obtained above under pressure and heat. The bond between stainless steel and FRP was excellent and the panel had the following advantages over conventional steel or uncoated SMC panels:

a. The outer surface of the SMC requires minimal maintenance.

b. The inner side is well known to be desirable for the food industry and is a reliable corrosion resistant side.

c. The inner surface is opaque and therefore SMC does not lose mechanical properties or bubbles even after long contact with water.

d. The inner side does not break when a large impact load is applied to the outer side.

The trays are shaped by cutting the edges and welding them, but they can also be made by stretching the metal.

Similar processes can be used to make circuit boards, filler plates, container panels, etc. of automotive body accessory prints.

EXAMPLE LIX

The following method can be used to make a dashed metal pipe.

A sheet of thin stainless steel (0.25 mm thick), 12 inches wide, was threaded around a 12 inch diameter shaft with an overlap of 1 inch. The seam of the overlap was sealed using CRODAGRIP 14-00300 (2 pot polyurethane).

The entire surface of the stainless steel was then covered with the same 2 pot polyurethane and dried to give a layer thickness of 0.25 mm.

A 5 mm thick reinforced layer was spirally wound on a previously prepared surface of stainless steel by impregnating a glass fiber coarse (coarse yarn) impregnated with appropriately catalyzed and accelerated (CRYSTIC 272 (unsaturated polyester resin based on isophthalic acid)). Got it.

The resin of the synthetic agent thus formed was cured at ambient temperature and then the pipe was removed from the shaft.

Thin stainless steel sheathed liners provide a complete barrier to a variety of different chemical environments and structural robustness is provided by rolling the FRP.

Chemical tanks can be prepared using a similar method.

Example LX

The dashed metal conduits and pipes are manufactured by another method, in which a stainless steel sheet of 0.25 mm thickness and 36 inches in width is connected by length using overlapping seams, and then the metal clop is Crodagrip 14-00300 (2 pot Polyurethane). An 11-inch diameter metal liner was supported by a shaft and the outer surface was covered with a polymer containing a polyvalent acrylate at the end and containing a urethane bond, which was accelerated by the appropriate auctioning. . The first coated layer was cured and then spirally wound onto the surface of the coated metal with the appropriately catalyzed accelerated DERAKANE 411-45 impregnated to obtain a reinforced layer having a thickness of 5 mm. The resulting synthetic resin was cured at ambient temperature, and then the 12-inch diameter stripped metal pipe manufactured according to the previous method was removed from the shaft.

Example LXI

Larger diameter pipes and tanks can be made by connecting one or more sheets of metal in length to length. This method can be achieved by using a fold stitching pistol, for example ATLAS COPCO Tagger 310 and a PTFE tape connecting film between the metal surfaces and by folding the connected flanges before treating with a suitable adhesive. Thus, a 36 inch wide internal stainless steel was connected in length as described above to obtain a body of a circular tank approximately 45 inches in diameter. It was placed on an axis and the outer surface was degreased with a solvent and then coated with INDASOL MS410 MS419 NF. When the coating layer was dry, the surface of the steel coated with glass fiber crumbs impregnated with the appropriately catalyzed accelerated CRYSTLC 272 was rolled up to produce a reinforced layer having a thickness of 5 mm. The resulting composite material was cured at ambient temperature and then the stripped metal tank prepared according to the previous method was removed from the shaft.

Example LXII

A thin aluminum sheet with a thickness of 0.45 mm was polished and degreased, and then the sheet was coated with a polymer containing a urethane bond at the end of the polyvalent acrylate at 200 g / m2. It was accelerated to receive. It was cured and then, by weight ratio, CRYSTIC 272 resin containing 33% FILLITE (silica hollow core) was moderately catalyzed to accelerate and poured onto the sheet to a depth of 10 mm.

This layer of the resulting composite was cured at ambient temperature and then covered with a layered glass with chopped strand mat (450 g / m 2) and impregnated with catalyzed accelerated CRYSTIC 272. The metal laminates thus produced are used as building panels for buildings with aluminum surfaces that provide good durability.

Example LXIII

Two stainless steels were degreased with solvent, treated with INDASOL MS 419 NF and dried. One sheet molding compound was sandwiched between the two treated surfaces and the resulting composite was cured under heat and pressure. The sheet coated with metal with double sides showed good adhesion to all interfacial bond lines.

Other metals can be used on each side to meet different environmental conditions.

Example LXIV

One piece of stainless steel (0.25 mm thick) was degreased with a urea and treated with INDASOL MS 419 NF and dried. A CRYSTIC 272 with a sheet-to-fiber ratio of 1: 1 in KEVLAR reinforcement (300 g / m2) of six layers of fabric was placed on the previously coated steel. The resulting composite was cured at ambient temperature and then the material thus obtained was stronger and harder than glass-reinforced thin plates, due to the good properties of KEVLAR fibers inherently.

Example LXV

The resin-processed thin stainless steel sheet was pressed and stretched into the shape of a car lid. It was degreased using a solvent and then the inner side was coated with CRODAGRIP 14-00300 at 200 g / m 2 and then cured. In addition to being shaped, the coated steel was placed in a two-part mold and the required amount of continuous stranded fiberglass mat made for the mold was placed on the coated side.

After the mold was sealed, accelerated CRYSTIC 272 (unsaturated polyester resin) was injected into the mold until all the air contained in the mold was pushed out. The injection of the resin was stopped and the resin of this composite was cured at ambient temperature. The mold was opened to obtain a FRP lid with a beautiful stainless steel surface that had good adhesion to the FRP and had been subjected to a resin process.

In the previous embodiment, various products have been described using brand names, which are each registered as trademarks of the following companies.

CRYSTIC-Scott Bader Company Limited.

DERAKANE-Dow Chemical Company.

TENAXATEX-Williams Adhesives Limited.

INDASOL-IndustrialAdhesives Limited.

INDATEX-Industrial Adhesives Limited.

PERMABOND-Permabond Adhesives Limited.

CRODAFIX-Croda Adhesives Limited.

CRODAGRIP-Croda Adhesives Limited.

NUTRIM-Aluminium Developments Limited.

IGETABOND-Sumitomo Chemical Company Limited.

KEVLAR-EI du Pont de Nemours Inc.

Claims (19)

A composite material for providing a product using a metal plywood made of a heat curable resin, comprising: a metal face and a curable heat curable resin, and a metal face between the metal face and the resin, and a heat curable resin. A composite material consisting of a single layer of adherent adhesive material, which together forms an adhesive bond during the curing of the aforementioned resin. The synthetic material according to claim 1, wherein the adhesive material is effective when cold-hardening the aforementioned resin. The composite material of claim 1 wherein the adhesive material is effective at high temperature curing of the aforementioned resins. The composite of claim 1 wherein the adhesive material is cured before placing the heat cured resin thereon. The adhesive material of claim 1, wherein the adhesive material contains a polyurethane bond and additionally contains a heat curable resin, which may contain an acrylic bond or an end group, and an acrylic resin, an epoxy resin, an unsaturated polyester, and a vinyl acetate residue. A composite material which is a heat curable resin selected from polymers. The composite of claim 5 wherein the heat curable resin is selected from acrylic, urethane and urethane / acrylic resins. The synthetic material according to claim 2, wherein the adhesive material is selected from epoxy resin nitrile rubber, acrylic resin and urethane resin. The composite of claim 1 wherein said curable thermosetting resin comprises reinforcing fibers. The composite material of claim 1, wherein the metal surface is selected from stainless steel, mild steel or galvanized steel, aluminum, copper, brass, phosphorus, bronze, zinc, nickel, tin, titanium, molybdenum, or chromium. Curable heating in a product using a metal plywood of heat curable resin comprising a metal face and a hardened heat curable resin layer and a layer of adhesive material between the metal face and the resin The product is formed by placing a curable resin on a metal coated with an adhesive material and curing the curable heat curable resin, wherein the adhesive material used can adhere to the metal during curing and also with the heat curable resin. Metal laminate product that can be bonded. The metal laminate of claim 10, wherein the heat curable resin layer comprises reinforcing fibers. In a method of manufacturing a product using a metal plywood, a layer of an adhesive material capable of adhering to the metal surface is prepared on a metal surface, and a curable heat curable resin is placed on the adhesive layer. A method of manufacturing a metal laminate product comprising the steps of preparing the metal laminate product described above by bonding an adhesive material to the resin by curing the heat curable resin. The method of claim 12, wherein the curing step is a cold curing step. The method of claim 12, wherein the adhesive material is selected from epoxy resins, nitrile rubbers, acrylic resins, and urethane resins. The method of claim 12, wherein the curing step is a high temperature curing step. The method of claim 15, wherein the adhesive material is a thermoplastic material which is a high temperature soluble adhesive in the form of a discontinuous layer. 13. The method of claim 12, wherein the layer of adhesive material is dried or cured prior to placing the curable heat curable resin thereon. 18. The method of claim 17, wherein the layer of adhesive material is fully cured before placing the curable heat curable resin thereon. 19. The method of claim 18, wherein the curing step is an internal temperature curing step.