HK1042067A1 - Method of fabricating a composite organic membranous substance - Google Patents

Description

Method for manufacturing composite organic film material

The present invention relates to a method for producing a composite organic film material comprising spraying a net-like or rod-like material comprising a film-like organic resin and a net-like or rod-like material with a solventless two-component type curable resin, and a method for corrosion-proofing a concrete substrate comprising using the composite organic film material.

The composite organic film material is composed of materials of not less than two components, namely resin, reinforced other auxiliary materials and the like. Heretofore, composite organic film materials have been widely used as reinforced resin films. For example, currently available glass fiber reinforced organic films and reinforced lined organic films.

Known methods for manufacturing a glass fiber-reinforced organic film include a reaction injection molding method (R-RIM method) in which a previously mixed reaction resin composition containing glass filaments is cast in a mold, and a reaction injection molding method (S-RIM method) in which a glass cloth or mat is placed in a mold in advance and then the reaction resin composition is poured into the mold.

In the R-RIM method, the glass filaments are oriented in the resin flow direction to be injection-molded, and sufficient strength is obtained in the orientation direction thereof, but in the direction perpendicular to the orientation of the glass filaments, a reinforcing effect is not actually expected. In the S-RIM method, a uniform distribution of strength can be achieved without local variation in the strength distribution due to orientation enhancement, but this method requires a large injection molding apparatus/metal mold.

Both of these methods can use nearly large equipment/metal molds for mass production of the same product, but are not at all suited for small volume production of multiple products. Also, there is a limit to the size of the product to be produced, and thus a large-sized product cannot be manufactured.

For the production of organic membranes lined with reinforcements for waterproofing, corrosion protection, reinforcement, and/or prevention of collapse (slide down) of concrete structures, FRP lining methods are known which use matrix resins such as vinyl ester resins, polyester resins, epoxy resins, and the like, and reinforcements such as glass cloth/mats, carbon filament cloth/mats, aramid filament cloth/mats, and the like. These methods always use cloth or pads as lining material.

Conventional lining methods include impregnating a reinforcing lining material with a resin that forms a resin film lined with reinforcement. In this method, the resin used must have a low viscosity in order to be impregnated efficiently. However, a drawback inherent in low viscosity resins is poor film forming properties. Therefore, there is a continuing need to address the technical problem of coordinating the conflicting requirements of such low viscosity and good film forming properties. The conventional method for solving the above problems is to compound a low molecular weight monomer or add an organic solvent to a resin composition to adjust the viscosity of the resin, and perform the following four steps of i) applying the resin composition, ii) superimposing a reinforcing liner on the resin, iii) impregnating the liner with the resin composition, iv) finally applying the resin composition. In this method, volatile components and organic solvents must be used, but these substances are hazardous to health and the environment. Due to this additional disadvantage, this method involves many steps as described above. And the conventional lining method is hardly applied to a high-viscosity resin composition.

Problems encountered in the prior art when applied to concrete structures, such as a significant decrease in adhesion of resin films with reinforcement to concrete when moisture is present. Therefore, when the surface of concrete is covered with an organic material to inhibit corrosion, the water content of concrete is usually controlled to about 8% or less, and in addition, a primer layer (undercoat layer) is interposed between the surface of concrete and the organic coating layer. However, at a construction site where various restrictions are imposed, it is difficult to control the water content of concrete to 8% or less. Moreover, when the concrete structure is rich in water or exposed to dew point condensation conditions, even the application of the primer does not ensure sufficient adhesion between the concrete and the resin coating.

Of course, the above problems are present not only in the application of conventional lining techniques, but also in the use of corrosion protection systems (polyurea resins are sprayed directly onto the concrete surface).

The above problem is a serious drawback when working concrete surfaces on a construction site. For example, it takes a long time and is expensive to completely dry the concrete surface with a heater having a blower device, apply a primer, and perform the above four steps. Therefore, this method cannot be selected in the case of works for renovation with a relatively short contact time, for example in the case of renovation of sewage systems which are interrupted only for a few hours a day. Moreover, it is not uncommon for insufficient drying to result in foaming, swelling or peeling of the applied film material.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a novel method for manufacturing a composite organic film material using a two-component type curable resin in a web-or rod-like material and without solvent, and a method for preventing corrosion of a concrete substrate without causing defects such as foaming, swelling or peeling even when the surface of the concrete is wet and is performed in a short time.

The invention relates to a method for manufacturing a composite organic film material, which comprises a film-shaped organic resin and a net-shaped or rod-shaped material.

The method comprises the steps of coating a solvent-free two-component curable resin in a sheet form on a net-shaped or rod-shaped material by two-component collision mixed spraying, and curing the resin to form a film-shaped organic resin integrated with the net-shaped or rod-shaped material.

The invention relates to a composite organic membrane material prepared by the method.

According to this method, a net-like or rod-like material is fixed to the surface of a substrate in advance, and then a composite organic film material is formed on the surface.

The invention also relates to a method of inhibiting corrosion in concrete.

The method comprises fixing a web or rod material in situ on a concrete surface, applying a solvent-free two-component curable resin to the web or rod material by two-component impingement mixing spray, and allowing the resin to cure, thereby forming a thick composite film organic resin comprising at least a portion of the material on the concrete surface.

The inventors have found that when a fast-curing solventless two-component curable resin is sprayed directly onto a web-like or rod-like material placed on a flat surface, the voids of the material are completely filled with the resin and, in addition, the coating covers not only the coated surface of the web-like or rod-like material but also the opposite surface thereof. The present invention has been completed on the basis of the above findings.

FIG. 1 is a schematic front sectional view of a composite organic film material of the present invention.

The present invention is described in detail below.

The method for preparing composite organic membrane material of the invention adopts double-component collision mixed spraying, and applies solvent-free double-component curable resin in sheet form on the reticular or strip material, and cures the resin, thus preparing a membrane material synthesized into a whole.

The mesh material is not particularly limited in its raw material, shape or structure, but may be appropriately selected depending on the application. For example, for the feedstock, such as a mesh screen which may be selected from iron, aluminum, stainless steel, and other metals; a mesh material of inorganic fibers such as glass fibers, carbon fibers, and the like; a network material of organic fibers such as aramid fibers; a net material of various other synthetic resins such as polyvinyl chloride, polyethylene, polyester, and the like; or various natural materials such as a net material of plant fiber and the like. The shape of the device can be any plane or curved surface. For example, the structure may be a structure in which a mesh is woven from one fiber or thread, a structure in which a plurality of wires or rods are arranged in a lattice and bonded at intersections, a structure in which a lattice is drawn by cutting a sheet at parallel multiple points, a structure in which a synthetic resin or the like is molded into a lattice, and holes in a lattice are punched in the sheet.

The plurality of rod-shaped materials may be arranged on a plane. The rod material is not particularly limited, but may be appropriately selected depending on the intended use. For example, it may be a rod-like material including any of the above materials.

In the present invention, the form of integrating the resin with the net-like or rod-like material is not particularly limited, and various forms are possible. For example, the form illustrated in FIG. 1(a), wherein the applied resin penetrates through the meshes or voids of the web material, protrudes a distance on the opposite side of the coated web material, so that the web material is partially or fully embedded in the resin, and thus, the web or rod-like material serves as a core; a form as shown in fig. 1(b) and (c) in which the applied resin penetrates through the meshes or voids of the material, locally protruding on the opposite side of the material, so that the material is partially surrounded or embedded by the resin; as illustrated in fig. 1(d), in which a resin is applied to both sides of a net-like or rod-like material to embed part or all of the material, which serves as a core.

The mesh size of the mesh material and the gaps of the rod-like material are not particularly limited as long as they are suitable for the purpose of the present invention. However, in practice, it is generally important to pay attention to the spray conditions and the properties of the resin, for example, the application viscosity of the resin, and to select the mesh size or the voids so as to spray the resin in a sheet form on the net-like or rod-like material while the resin is integrated with the net-like or rod-like material. For a mesh material, for example, a mesh size of not more than 10 mm is preferable because it is easy to form an uninterrupted continuous film. There is no specific lower limit to the mesh size of the mesh material or the voids of the rod-like material. However, since it is necessary to integrate the film-like organic resin, the size of the mesh or the space is preferably such that at least a part of the resin protrudes into the space of the mesh or the space. The mesh size of the mesh material or the size of the interstices of the rod-like material is preferably in the range of 1-5 mm, most preferably in the range of 3-5 mm.

The web or rod material preferably maintains its structure and alignment, allowing the resin to be applied in sheet form. Thus, the material may be secured to the support or a support provided with the material to maintain its structure or alignment, as desired.

There is no particular limitation on the solvent-free two-component curable resin as long as it forms a film-like organic resin when sprayed. Such compositions generally comprise a main component and a curing agent component which can be mixed at the time of spraying to initiate the curing reaction, and preferred compositions comprise an isocyanate component (A) and a polyamine and/or polyol component (B). Film-like organic resins that can be produced using a polyamine as the component (B) include polyurea resins. The film-like organic resin produced using a polyol as the component (B) includes a polyurethane resin. On the other hand, when the component (B) is a mixture of polyamine and polyol, the film-like organic resin obtained comprises a polyurethane/polyurea resin film.

The isocyanate component (A) includes organic polyisocyanates, isocyanate prepolymers, and mixtures thereof.

The organic polyisocyanate is not particularly limited, but may be known polyisocyanates such as aromatic polyisocyanates, aliphatic polyisocyanates, and the like.

The above aromatic polyisocyanate is not particularly limited, but may include carbodiimide-modified liquid diphenylmethane diisocyanate or a partial prepolymer thereof; 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, and mixtures thereof (hereinafter collectively referred to as TDI); diphenylmethane-4, 4' -diisocyanate (hereinafter collectively referred to as MDI), polymethylene polyphenyl polyisocyanate; and their carbodiimide-or biuret (biuret) modified products.

The above aliphatic polyisocyanate is not particularly limited, but may include dicyclohexylmethane-4, 4' -diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isocyanurate-modified products of the above diisocyanates or modified products of carbodiimide.

The above-mentioned isocyanate prepolymer includes a partial prepolymer obtained by reacting some of the isocyanate groups in an organic polyisocyanate such as those described above with a polyol having a number average molecular weight of 200-8000.

The isocyanate prepolymers described above can be prepared by heating any of the above-described organopolypolyesters in the presence of a polyol at 70-80 ℃ under nitrogen for several hours to react at least a portion of the isocyanate groups with the polyol. The above-mentioned polyol is not particularly limited, but includes, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 10-decanediol, 1, 2-cyclohexanediol, glycerol, 1, 2, 6-hexanetriol, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane and the like; and polyether-polyols obtained in the polyaddition of a polyol such as pentaerythritol with one or more epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like. In the present invention, the molecular weight of the polyol is preferably 200-. These polyols may be used alone or in suitable mixtures.

In the practice of the present invention, there is no particular limitation on the polyamine which can be used as the component (B), and it is preferable to use a mixture of polyoxyalkylene-polyamine (a) and reactive aromatic diamine (B) which has no electron-withdrawing group on its aromatic nucleus and an alkyl substituent of not more than 5 carbon atoms at a position near the amino group, for example, excluding tolylenediamine.

The polyoxyalkylene-polyamine (a) may be, for example, a compound having a number average molecular weight of 200-10000, containing at least two aliphatic amino groups per molecule. For example, such a compound can be produced by reacting a terminal hydroxyl group of a polyoxyalkylene polyol having at least two hydroxyl groups with ammonia in the presence of a hydrogenation-dehydrogenation catalyst at high temperature and high pressure.

The above polyoxyalkylene-polyamine (a) includes polyoxypropylene diamine such as Jeffamine D-2000(huntsman specialty Chemicals; amine equivalent about 1000); polyoxypropylene triamines such as Tecslim TR-5050(Huntsman specialty Chemicals; amine equivalent about 1930); jeffamine T-403(Huntsman Speciality Chemicals; amine equivalent about 160), and the like.

It is also effective to use a modified polyoxyalkylene polyamine which is modified by converting at least a part of primary amino groups in the above polyoxyalkylene polyamine (a) into secondary amino groups by Michael addition reaction with an unsaturated hydrocarbon of the general formula,

CH₂(R) -Y wherein R represents hydrogen or methyl; y represents an electron withdrawing group.

The electron-withdrawing group Y is not particularly limited, but includes ester residues, ketone residues, cyano residues, substituted or unsubstituted amide residues, sulfonic acid residues and sulfonic acid ester residues.

The above-mentioned unsaturated hydrocarbon group is not particularly limited, but includes esters of acrylic acid such as n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate, lauryl acrylate, stearyl acrylate, propyl acrylate and the like; esters of methacrylic acid such as n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, lauryl methacrylate, stearyl methacrylate, propyl methacrylate, etc.; acrylonitrile; (ii) acrylamide; n, N' -dimethylacrylamide; ethyl vinyl sulfone; methyl vinylsulfonate, ethyl vinylsulfonate, and the like.

The above-mentioned reactive aromatic diamines (b) which have no electron-withdrawing group on the aromatic nucleus thereof but have an alkyl substituent of not more than 5 carbon atoms at a position close to the amino group include, in addition to tolylenediamine, 1, 3-dimethyl-2, 4-diaminobenzene, 1, 3-diethyl-2, 4-diaminobenzene, 1, 3-dimethyl-2, 6-diaminobenzene, 1, 4-diethyl-2, 5-diaminobenzene, 1, 4-diisopropyl-2, 5-diaminobenzene, 1, 4-dibutyl-2, 5-diaminobenzene, 1, 3, 5-triethyl-2, 4-diaminobenzene, 1, 3, 5-triethyl-2, 6-diaminobenzene, 1, 3, 5-tripropyl-2, 6-diaminobenzene, 1-methyl-3, 5-diethyl-2, 4-diaminobenzene, 1-methyl-3, 5-diethyl-2, 6-diaminobenzene, and the like. These compounds may be used alone or in a suitable combination.

It is also possible to use modified polyamines which are modified by converting at least part of the primary amino groups of the reactive aromatic diamines (b) (other than toluene diamine) which have no electron-withdrawing group on the aromatic nucleus thereof and an alkyl substituent of not more than 5 carbon atoms at a position close to the amino group into secondary-human amino groups by Michael addition reaction with the unsaturated hydrocarbon.

As for the polyamine used for the component (B), the polyoxyalkylene polyamine (a) is blended with an active aromatic diamine (B) (excluding tolylenediamine) having no electron-withdrawing group on its aromatic nucleus but having an alkyl substituent of not more than 5 carbon atoms at a position near the amino group at a blending ratio of 15 to 100 parts by weight of (B) to 100 parts by weight of (a). If the amount of (b) is less than 15 parts by weight, the film-like organic resin will be very soft and semi-tacky and the film material product will have poor quality properties. On the other hand, if it exceeds the upper limit of 100 parts by weight, the film-like organic resin is hard and brittle, and the film material product cannot be used. A more preferable range is 20 to 40 parts by weight.

On the other hand, there is no particular limitation on the polyol used for the component (B). In order to control the physical properties of the film-shaped organic resin, a low molecular weight polyol (number average molecular weight: 62 to 1000) and a high molecular weight polyol (number average molecular weight: 1000 to about 10000) as the main components of the organic resin layer can be used.

The low molecular weight polyols may be those polyols described above for preparing isocyanate prepolymers, having molecular weights within the ranges described above. On the other hand, the high molecular weight polyol is preferably a polyether polyol or a polyester polyol. Polyether polyols include those compounds described above as examples. Polyester polyols include the various polyester polyols produced by the reaction between aliphatic dibasic acids and aliphatic dihydric alcohols and polycaprolactone polyols. Such polyester polyols include polyols such as ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, polyether polyols, bis (hydroxyethyl) terephthalate, glycerol, trimethylolpropane, pentaerythritol, mixtures thereof, and the like, with polybasic acids, especially dibasic acids or ester derivatives thereof such as succinic acid, glutaric acid, adipic acid, the dimethyl esters of these acids, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, dimethyl terephthalate, and the like. Polyesters prepared by polymerizing cyclic ester lactones, such as caprolactone, in the presence of a polyol may also be used.

The solvent-free two-component curable resin of the present invention comprising the isocyanate component (a) and the polyamine and/or polyol component (B) may further comprise a third component. For example, conventional plasticizers, flame retardants, fillers, stabilizers, colorants and other adjuvants may be used as desired. The third component may be added directly to said component (A) or (B).

In the practice of the present invention, the web or rod material is sprayed with a solventless two-part curable resin using a two-part impingement spray technique. Spraying on one or both surfaces of the net-shaped material and the rod-shaped material. The film-like organic resin is formed by the following method; the impingement mixing spray technique is used in such a way that two components of the two-component curable resin, for example the isocyanate component (a) and the polyamine and/or polyol component (B), are sprayed out only after the curing reaction has proceeded to such an extent that the particles are still in a suspended state, the components are applied in sheet form to the web-or rod-shaped material and allowed to cure. At the application temperature, the isocyanate component (a) and the polyamine and/or polyol component (B) must remain liquid. Preferably, a high pressure dual component impingement mixing spray system is used to perform the dual component impingement mixing spray.

The high pressure two-component impingement mixing sprayer described above is not particularly limited, but includes such proportional delivery devices as Gusmer (U.S.) H-2000, Gusmer (U.S.) H-3500, Gusmer (U.S.) FF-1600, and the TohoMachinery Industry two-component high pressure delivery mixer, model HF-100. Further, there are high-pressure two-component mixing guns having a mechanical self-cleaning function, a Gusmer (U.S.) "GX-7 gun", a Gusmer (U.S.) "GX-7-400 gun", and the like. There are also spray guns equipped with air cleaning mechanisms, Glass-Craft (u.s.) "propeller guns".

As for the mixing ratio of the above-mentioned isocyanate component (A) to the above-mentioned polyamine and/or polyol component (B), the equivalent ratio of the amino group and the hydroxyl group in the above-mentioned component (B) to the isocyanate group in the above-mentioned component (A) is preferably from 1/0.7 to 1/1.5, more preferably from 1/0.9 to 1/1. Beyond this range, the curing reaction cannot be sufficiently performed, and for this reason and others, the physical properties of the film-like organic resin are adversely affected.

In the present invention, the preferred solventless two-part curable resins, when applied by the two-part impingement-mix spray technique, have a tack-free time, i.e., the time required to dry to the point that no fingerprints remain, of no more than 3 minutes. If the tack-free time is more than 3 minutes, the resin is difficult to apply in sheet form to a web or rod-like material. Depending on the end use of the film material, shorter tack free times may be required in some cases. For example, a web or rod material is fixed in place to cover the surface of at least one substrate selected from concrete, mortar or rock, and then a curable resin is applied to the material to produce a thick composite organic film material as described above, preferably having a tack-free time of not more than 20 seconds, more preferably not more than 10 seconds, from an engineering standpoint. By adjusting the kind and amount of the compound of the above-mentioned component (B), and the amount of the above-mentioned third component such as a plasticizer, the tack free time can be controlled. For example, selecting a polyamine as the above-mentioned component (B) can shorten the tack-free time.

In the present invention, the resin mixed in the mixing gun is sprayed at an angle of 45 to 90 degrees with the above net-like or rod-like material. If the resin collides with the above-mentioned material at an angle of less than 45 deg., the resulting film material is not uniform. A more preferred impact angle is 75-90.

In the present invention, when the high-pressure two-component collision mixing spray system is used, the collision mixing pressure is preferably 6 to 15 MPa.

Further, the distance between the rod-like or net-like material and the mixing lance is preferably about several tens of centimeters to 1 meter.

In the present invention, the thickness of the composite organic film material is not particularly limited, but may be appropriately selected depending on the intended use or the kind of the net-like or rod-like material to be used. In the case of cured resin applied in sheet form, the resin may be applied to the web or rod material at any desired thickness between 0.5 and 10 mm, and even thicker. The net-like or rod-like material is integrated with the resin, and the thickness of the prepared composite organic film material is generally larger than that of the resin film formed on the net-like or rod-like material. If the thickness of the resin film is less than 0.5 mm, the durability of the film material is insufficient. If it exceeds 10 mm, the cost of resin consumption becomes unacceptably high. Therefore, the thickness of the resin film is preferably controlled to the above range.

In the practice of the present invention, the web-or rod-shaped material is preformed into the shape of an object of a film material, such as a flat sheet, a curved sheet, or a three-dimensional shape, and then a curable resin is directly sprayed on the thus-formed material to prepare a composite organic film material having a desired shape. The use of the film material is not particularly limited, and typical examples thereof include organic masks and catheters. Therefore, even if the number of lots is small, a large-sized film material having a complicated shape can be manufactured at low cost.

The web or rod material may be fixed in place by pre-coating the substrate surface. The method of fixing is not particularly limited, and may be, for example, bolt-nut fixing or weld fixing, depending on the intended application. With this mounting and fixing, a composite organic film material firmly fixed to the surface of the substrate can be produced. The surface of the substrate is not particularly limited and may be, for example, at least one selected from the group consisting of concrete, mortar and rock. The function of the membrane material is not particularly limited, but includes corrosion inhibition, waterproofing, reinforcement, collapse prevention, and the like of various structures such as concrete or mortar buildings, concrete pipes or water pipes, and other structures. The invention is also applicable to inhibiting corrosion, waterproofing, preventing water leakage, strengthening, preventing collapse or cave-in of various surfaces of civil engineering, such as cliffs, tunnels, ponds, and waste disposal facilities.

A method for inhibiting corrosion of concrete is generally used which comprises first fixing the mesh or rod material in situ on a concrete surface, spraying a solvent-free two-component curable resin onto the mesh or rod material using a two-component impingement-mix spray technique, and allowing the resin to cure to form a composite organic film material comprising the mesh or rod material partially embedded therein on the concrete surface. For example, the invention can be applied to the anticorrosion treatment of the inner wall of a drainage pipe or a water inlet pipe in the repair engineering of a sewage system. This can be done by fixing a cylindrical or semi-cylindrical net-like material to the inner wall of the drain pipe, or fixing a rod-like material assembly fixed in parallel to a pre-formed frame having a shape complementary to the inner wall of the drain pipe, and applying the resin. In this way, the composite organic film material of the present invention can be firmly fixed to the concrete surface even if water is present on the concrete surface, and thus the work can be completed in a relatively short time.

In the method of the present invention, the composite organic film material is fixed on a substrate such as concrete, and is integrated into a whole by a net-shaped or rod-shaped material fixed on the surface of the substrate. Therefore, even if water is present, adverse effects due to a decrease in adhesion between the resin and the concrete surface can be prevented, covering, corrosion prevention, waterproofing or reinforcement work can be conveniently performed in a short time without causing defects such as foaming, swelling or peeling, etc., and without being affected by surface water or moisture of the concrete structure and other factors. Moreover, since the method of the present invention is a solventless method, it does not harm human health and environment.

The present invention provides a method by which such a large-sized film material having a complicated shape can be easily produced at low cost. Furthermore, with this method, high quality covering, corrosion prevention, waterproofing or reinforcement and other works on the construction site can be conveniently performed in a short time without being affected by surface water or moisture of the concrete structure and other factors. Moreover, the method of the present invention is quite safe for human health and the environment.

Examples

The present invention is illustrated in more detail by the following examples without departing from the scope of the invention.

Example 1

A solvent-free 2-component polyurea resin system (Toughguard R-G, Nippon Paint) comprising an isocyanate component (a) and a polyamine component (B) is used as a solvent-free two-component curable resin. A two-component collision-mixing nebulizer (Gusmer) was used as the nebulizer. The collision-mixing ratio of component (A)/component (B) was about 1: 1 (volume ratio), and the NCO index, i.e., the ratio of amino groups in component (B) to isocyanate groups in component (A), was about 1.05. A GX-7 gun from Gusmer was used as the mixing lance. The material temperature of the components A and B is 55 +/-5 ℃, and the transmission pressure condition is 7-12 MPa. A stainless steel mesh having a mesh size of 1 mm was used as the mesh material. The mesh material was placed on a level ground and the spray gun was fixed about 30 cm from the mesh material, with the resin transfer direction held at right angles to the mesh material surface, spraying one side of the mesh material.

On the coating surface of the reticular material, the thickness of the prepared polyurea resin film is 2-3 mm. 5 seconds after coating, the applied resin became dry and tack-free.

The coated surface is provided with a fine uneven pattern corresponding to the mesh of the web material, but the coating is continuous and safe, without pits, creases, discontinuities or cracks. Although the resin film is formed on the coated side of the web material, a very small amount of resin penetrates the opposite side of the web material. The resin film cannot be torn off, and the mesh material is integrated with the resin film. Careful observation revealed that the screen material was largely covered by a resin film around the protruding points of its intersection.

Examples 2 and 3

The procedure of example 1 was repeated to produce a composite organic film material except that the mesh size of the mesh material was 3 mm and 5 mm, respectively. On the coated side of the mesh material, polyurea films of 2 to 3 mm and 3 to 4 mm were formed, respectively. In both cases, a resin film having a thickness of 2 to 3 mm was also formed on the opposite surface of the web material.

In both cases, the coated surface is provided with a fine uneven pattern corresponding to the screen opening, but the coating is continuous and safe, without pits, creases, discontinuities or cracks. The resin covers not only the screen material but also the opposite surface thereof, most of the material being embedded in the resin, and the resulting composite organic film material contains the screen material as a core.

Example 4

The procedure of example 1 was repeated to produce a composite organic film material except that the mesh size of the mesh material was 10 mm. A polyurea resin layer with a thickness of 4 to 6 mm is formed on the coated surface of the material.

The coated surface is provided with a fine uneven pattern corresponding to the mesh, but the coating is continuous and safe, without pits, creases, discontinuities or cracks. However, although the resin is partially formed on the reverse side from the mesh, the resin covers only the coated side of the mesh material, and does not cover the reverse side. This phenomenon is probably because the mesh is large, and the resin exposed on the back surface is cured at the front end and is not gathered into a whole. The mesh material and the resin film are integrated without being separated from each other. Careful observation revealed that the screen was covered mainly with a resin film around the protruding points where it crossed.

Example 5

A composite organic film material was produced by repeating the procedure of example 1 except that the mesh size of the material was changed to 3 mm and the tack-free time of the resin was adjusted to 20 seconds.

The coated surface had a fine three-dimensional surface corresponding to the mesh, but the resin film was continuous and safe, with no pits, creases, discontinuities or cracks. The resin covers not only the coated surface but also the opposite surface, and most of the mesh material is embedded in the resin film as a whole.

Example 6

A solvent-free two-component curable polyurethane/polyurea resin was prepared in the same manner as in example 1, using the same isocyanate component (A), except that the polyamine of component (B) was partially replaced with a polyol, so that the tack-free time of the system was adjusted to 120 seconds. Then, a composite organic film material was produced in the same manner as in example 1, using a mesh material having a mesh size of 3 mm.

The coated side carries a fine uneven pattern corresponding to the mesh, but the film formed is continuous and safe, with no pits, creases, discontinuities or cracks. However, although the resin is locally formed on the reverse side, the resin only masks the coated side of the web material, leaving the reverse side uncovered. This phenomenon is presumably due to the fact that the applied resin is not deposited in sufficient quantity to cover the reverse side. The mesh material and the resin film are integrated without being separated from each other. Careful observation revealed that the screen was covered mainly with a resin film around the protruding points where it crossed.

Example 7

A solvent-free two-component curable polyurethane resin was prepared in the same manner as in example 1, using the same isocyanate component (A), except that the polyamine of component (B) was partially replaced with a polyol, and the tack-free time of the system was adjusted to 180 seconds. Then, a composite organic film material was produced in the same manner as in example 1, using a material having a mesh size of 3 mm.

The coated side carries a fine uneven pattern corresponding to the mesh, but the film formed is continuous and safe, with no pits, creases, discontinuities or cracks. However, although the resin is locally formed on the reverse surface, the resin covers only the coated surface of the mesh material, and does not cover the reverse surface. This phenomenon is presumably due to the relatively long tack-free time of the compound and the failure of the applied resin to deposit in sufficient quantity to cover the reverse. The mesh material and the resin film are integrated without being separated from each other. Careful observation revealed that the screen was covered mainly with a resin film around the protruding points where it crossed.

Comparative example 1

A composite organic film material was produced in the same manner as in example 1 except that the mesh size of the material was 15 mm.

The coated side does not present a continuous film, the resin cannot be applied to a web-like material in a sheet form, and therefore, a desired composite organic film material cannot be formed. It is considered that the resin cannot be applied to the web material in a sheet form because the mesh size to which the resin is applied is too large.

Comparative example 2

The amount of tin catalyst in the solvent-free two-component polyurethane resin used in example 7 was reduced to give a tack-free time of 30 minutes. This composition was coated on a material having a mesh size of 3 mm in the same manner as in example 1.

The coated side is not a continuous resin film, and the resin cannot be applied to a web material in a sheet form, and thus cannot form a desired composite organic film material. This phenomenon is probably because the tack-free time of the resin is too long for such a mesh size, and therefore the resin cannot be applied to the web in a sheet form.

Comparative example 3

An epoxy resin (Toughguard E top coat, Nippon Paint) was coated on the mesh material having a mesh size of 3 mm. The tack free time of the resin was 18 hours.

The coated side is not a continuous film, and the resin film cannot be applied to a web material in a sheet form, and thus, a desired composite organic film material cannot be obtained.

Claims (11)

1. A method of manufacturing a composite organic film material comprising a film-like organic resin and a web-like or rod-like material, the method comprising the steps of: a solvent-free two-component curable resin is applied in a sheet form to a web-like or rod-like material by two-component collision-mix spraying, and the resin is cured to form a film-like organic resin integral with the web-like or rod-like material.

2. A method according to claim 1, wherein the solventless two-part curable resin comprises an isocyanate component (a) and a polyamine and/or polyol component (B).

3. A method according to claim 1 or 2, further characterized in that the mesh size of the net-like material does not exceed 10 mm.

4. A method according to any of claims 1-3, wherein said solventless two-part curable resin has a tack-free time of no more than 3 minutes.

5. A method according to any of claims 1-4 wherein the film-like organic resin covers at least a portion of the web or rod material.

6. A method according to any one of claims 1 to 5, further characterised in that the method comprises fixing the mesh or rod material in situ on a substrate surface to be protected and then forming the composite organic film resin to cover the substrate surface.

7. The method of claim 6, wherein said substrate surface is at least one surface selected from the group consisting of concrete, mortar, and rock.

8. The method of claim 7, wherein said solventless two-part curable resin has a tack free time of no more than 20 seconds.

9. The method according to any one of claims 1 to 8, further characterized in that the two-component collision-mixing type spraying is carried out at a collision-mixing pressure of 6 to 15MPa using a high-pressure two-component collision-mixing type atomizer equipped with a mixing lance with a mechanical self-cleaning function.

10. A method of inhibiting corrosion in concrete, said method comprising fixing a mesh or rod material in situ on a concrete surface, applying a solvent-free two-component curable resin to said mesh or rod material by two-component impingement-mix spraying, and allowing the resin to cure, thereby forming a thick composite film-like organic resin comprising at least part of said material on said concrete surface.

11. A composite organic film material, producible by the method of claim 1.