DE69938308T2 - Composite and synthetic sill using this composite - Google Patents

Description

The The invention relates to a composite and a synthetic rail sleeper using the composite.

moldings made of fiber-reinforced thermosetting Foam that resembles natural wood in appearance and physical Properties same or higher Perform as natural wood, are used as construction materials used, which include building material, structural material, and threshold Belong plate material, the for moist places are used.

In general, the thermosetting foam molded articles of this type have a plate-like or rod-like main shaped body formed by the foamed and hardened thermosetting foam liquid, such as Japanese Patent Publication No. Sho 52-2421 and the Japanese Patent Laid-Open Publication No. Hei 5-23947 disclosed. Inside the main body, long fiber glass fibers are longitudinally arranged in parallel as reinforcing fibers and distributed generally in parallel.

These Moldings made of heat-curable Foam from the conventional Type have sufficient resistance to bending stress on, perpendicular to the longitudinal direction exercised is because the reinforcing fibers inside the main molding longitudinal arranged in parallel and distributed generally in parallel. she However, they have the disadvantage that they for example, when nailing lightly in a direction parallel to the reinforcing fibers Cracks or break, or the disadvantage that they have a low nail pull strength exhibit.

In view of this, a composite has been proposed in which surface layers comprising a thermosetting foam in which reinforcing fibers are arranged longitudinally parallel and generally parallel are laminated to both surfaces of a core layer comprising thermosetting foam in which no more than 50 wt .-% filler are dispersed (see. Japanese Patent Laid-Open Publication No. Hei 5-138797 ).

Short said, this composite is made with a layered structure, in the core layer of excellent compressive strength between the surface layers added is to thereby improved pressure resistance and better To produce nail behavior.

However, since this composite, as in 17 shown, having a structure in which between the filler 200 the core layer 100 and the filler 200 a thermosetting resin layer 300 is present, it has the disadvantage that its compressive strength and nail behavior are insufficiently improved.

In addition, it suffers from the drawback that the thermosetting resin layer may be subject to severe bending or repeated bending of the composite 300 gets destroyed.

Under consideration of these circumstances the present invention has been developed with the aim of a Composite, its compressive strength and nail behavior can further improve, as well as a synthetic threshold with use of the composite.

US-A-4083491 discloses a railway sleeper constructed of at least two individually different rail support blocks interconnected by a web system secured to the blocks. The blocks are made of hard, tough and weatherproof material, such. B. HDPE. The material may contain fillers or fibers. The web system is composed of separate side pieces attached to respective side surfaces of the blocks. The side pieces may be fiber reinforced plastic, such as. B. epoxy.

JP-A- discloses a composite comprising a thermosetting foam Nuclear material and in one piece on opposite Side of the core has laminated surface materials. The surface material consists of the same thermosetting Foam like the core material and is in the longitudinal direction fiber reinforced of the core composite. The density of the surface material is higher than that of the core material.

The The invention provides a composite as claimed in claim 1 set out below.

The thermosetting Surface layer resin can be a light filler contain.

The surface layer may have a density of at least 0.3 g / cm ³ to at most 1.5 g / cm ³ .

The surface layer can have a flexural modulus of at least 6000 MPa and a flexural strength of have at least 100 MPa.

Of the filler may have a mean particle size of at least 0.5 mm.

Of the filler can be measured on a particle size distribution curve, in the particle size on the Abscissa and a volume ratio of the filler per particle size to all fillers are plotted on the ordinate, have two or more peak areas, which make up at least 8% by volume and also has a size distribution on, at the most common particle size values in the smaller peak area of at least 8% vol. at most 0.7 times the most common particle size values in the larger peak area of at least 8 vol.%, Which is closest to the smaller peak area.

The Resin that forms the core layer can be a thermosetting one Be resin.

The Resin that forms the core layer may be a thermoplastic.

The synthetic resin forming the core layer may be a thermosetting polyurethane foam having a polyol equivalent of at least 230 to at most 1500 or a thermosetting polyurethane foam having a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500.

The Core layer can be formed by multiple core layers, the form a composite layer.

A the core layer forming composite layers may be a thermosetting Resin reinforced by long fibers becomes parallel in their longitudinal direction run, or a light filler containing thermosetting Resin reinforced by long fibers that are parallel in their longitudinal direction run.

The Core layer may have a compression shear strength DBa of at least 5 Have MPa.

The Core layer and the surface layer can through an intermediate layer, the foam-free thermosetting Resin or low-power foam, in one piece with each other be glued.

Of the Interlayer section may have a compressive shear strength of at least 6 MPa, or the surface layer and the core layer can both have a compressive shear strength of at least 6 MPa, when on the composite in one to the fiber direction of the long fibers the surface layer parallel direction acts a compressive force, so that a fracture surface in the Interlayer section may arise, the composite may have the physical property that either the surface layer or the core layer first breaks when the compressive force on the composite in the fiber direction of the long fibers of the surface layer attacks parallel direction, so that the fracture surface in the Interlayer section may arise.

In the intermediate layer can be a resin-impregnated film-like Material to be arranged.

The Core layer synthetic resin can be polyurethane foam, and the resin of the surface layer can be) polyurethane foam.

Of the Composite may have a total thickness of at least 100 mm, and a relationship between the thickness of the core layer and the total thickness of the surface layer, which covers the core layer in the thickness direction is in the range from 9/1 to 1/1.

The Core layer can be at least two layers of core layer forming Compositions, the filler and synthetic resin, and at least one layer of a core layer forming Composition with thermosetting Resin reinforced by long fibers between the two core layer-forming compositions at least two layers of core layer-forming compositions are incorporated and parallel in the longitudinal direction of the composite, with a ratio between the total thickness the core layer forming composition layer and the total thickness of the core layer forming composition layer in the range of 95/5 to 50/50 can lie.

The surface layer may be laminated to the core layer to cover at least two surfaces of the core layer, the composite may have a total thickness of at least 100 mm, and the thickness of the surface layer (FIG. 3 ) on the side to which a tensile force is exerted when the composite is bent in the thickness direction is at least 5% to at most 25% of the total thickness, and the thickness of the surface layer ( 3 ) on the side to which a compressive force is applied is at least 1.5% to at most 15% of the total thickness.

The surface layer can have four surfaces surrounded by the core layer and forms at least 10 vol .-% to at most 65 vol% of the total composite.

The Invention also provides a synthetic threshold providing a composite according to the invention having.

below the nature of the composites according to the corresponding claims will be described in detail.

The for the Core layer usable resins in the compositions according to claims 1 to 6 contain thermosetting Resins as in the composite of claim 7 and thermoplastic such as in the composite according to claim 8, but it may also be a mixture on thermosetting Resin and thermoplastic can be used.

The for the Core layer used thermosetting Although resins are subject to no particular restriction, but to the usable thermosetting Resins belong Resins before the reaction in liquid or powder form present and foamable are, for example, polyurethane resin, phenolic resin, unsaturated Polyester resin, diallyl phthalate resin, vinyl ester resin, epoxy resin, Urea resin, melamine resin, polyimide resin, polyamide-imide resin, acrylic resin, Natural rubber and synthetic rubber belong. These resins can be used in Combination of two or more resins are used.

The for the Although core thermoplastics used are not subject to any special restriction but useful thermoplastics include, for example, polystyrene, syndiotactic polystyrene, low density polyethylene, high density polyethylene, linear high-pressure polyethylene, polypropylene, hard polyvinyl chloride, Acrylic resin, ABS resin, aliphatic polyamide resin (nylon), polyethylene terephthalate, Polybutylene terephthalate, polyoxymethylene, polycarbonate, polyarylate, Polysulfone, polyethersulfone, polyetheretherketone and polyphenylene sulfide or a copolymer or mixture thereof. These substances can also foamable be.

From These thermoplastics also preferably have crystalline resins a melting point of at least 80 ° C, more preferably at least 120 ° C. on the other hand For example, non-crystalline resins preferably have a glass transition point of at least 80 ° C, stronger preferably at least 100 ° C. At a melting point and glass transition point, which is lower than these temperatures, it is possible to that yourself deteriorate the bending properties and the heat resistance properties can.

to Use in the surface material is preferably a filler to use, which has a thermal expansion coefficient has, which comes close to the long fibers.

The for the surface layer in the composites according to claims 1 to 4 used thermosetting Although resins are subject to no particular restriction, but to the usable thermosetting Resins belong the resins that are in liquid or powder form before the reaction present and foamable are; for example, polyurethane resin, phenolic resin, unsaturated Polyester resin, diallyl phthalate resin, vinyl ester resin, epoxy resin, Urea resin, melamine resin, polyimide resin, polyamide-imide resin and acrylic resin belong.

The thermosetting Foams used for the surface layer used contain thermally decomposable blowing agents, such as z. Azo compounds and sodium bicarbonate, foaming solvents, such as Freon, carbon dioxide and pentane, and thermosetting foam liquids including those from which as a by-product in the reaction and in curing gas arises. For example, can be harder or semi-rigid polyurethane foam, phenolic foam, low-power Polyester foam led become.

Polyurethane foam is particularly preferred because it has a relatively high mechanical strength Has strength and can form slightly closed cells during foaming and therefore has an excellent low absorption capacity.

Of the lightweight filler, in the surface layer the composite according to claim 2 is subject to no particular restriction, but to the usable light fillers belong for example powder / granules, foam particles and hollow particles, such as B. glass hollow particles, silica hollow spheres, fly ash hollow spheres, Shirasu hollow spheres (= microporous Glass), porous Glass, Expanded Slate, porous Ceramics, perlite, pear stone, vermiculite and synthetic resin. To the synthetic resins, as a light filler can be used belong the same hardener for thermosetting resins and crosslinked rubber like those used for the surface layer be used, and also crystalline thermoplastic resin with a higher one Melting point than the temperature at which the thermosetting resin hardened and non-crystalline thermoplastic resin having a glass transition point. In order to reduce the absorption rate of the composite, be preferably used closed cell fillers. The easy one Filler can be surface-treated with a silane coupling agent and the like.

In the composite according to claim 1 or 2, the surface layer preferably has a density of at least 0.3 g / cm ³ to at most 1.5 g / cm ³ . The reason for this is that too low a density of the surface layer tends to lower the flexural strength of the composite, while on the other hand too high a density of the surface layer tends to cause the composite to easily crack during nailing. The preferred density range will vary depending on the intended application of the composite. For example, for the use of the composite as a railway sleeper, the surface layer more preferably has a density of at least 0.6 g / cm ³ to at most 1.5 g / cm ³ . For the use of the composite material as a ramp material or floor material for a swim bridge, a roadway and a boat, the surface layer more preferably has a density of at least 0.3 g / cm ³ to at most 0.8 g / cm ³ .

In The composite according to claims 1 to 5, the long fibers are not specific to any particular configuration limited, as long as they are reinforcing fibers can be used. Examples of usable long fibers include Monofilaments, chemical cellulose fibrils (feathered fibers) and weaving yarn. Long fiber materials include inorganic and organic Materials, such. As glass, carbon and resin. Prefers be glass or carbon, which has a high reinforcing effect achieve. these can used singly or in combination of two or more.

Of the Proportion of in the surface layer Although not subject to any particular limitation, long fibers contained at least 5 vol.% to at most 40% by volume are preferred. Less than 5% by volume produce long fibers no reinforcing effects, such as B. in terms of bending strength. On the other hand, more than 40 vol.% long fibers in nailing the composite into one potential Rupture, parallel runs to the fibers.

When the thermosetting resin of the surface layer is a foamable material, the resin density is preferably at least 0.2 g / cm ³ . A resin density of less than 0.2 g / cm ³ leads to an undesirable reduction in flexural strength. There is no particular upper limit. An upper limit of a resin density of the surface layer is substantially equal to the value of the thermosetting foam which can be practically produced.

In the composite according to claim 3 contains the surface layer preferably at least 20 vol.% to at most 50 vol.% light Filler, to the above long fiber content and the resin density of the thermosetting Resin of foamable Material to match. At less than 20 vol% light filler cracks easily form in the surface layer during nailing. On the other hand, at more than 50% by volume of light filler the light fillers not even in that thermosetting Resin dispersed so that the possibility exists that the physical properties, such. B. the bending strength, itself can worsen.

In The composite according to claims 1 to 3 amounts to the flexural modulus of the surface layer is preferably at least 6000 MPa, as in the composite according to claim 4, more preferred at least 7000 MPa, or even more preferably at least 8000 MPa. The reason for this is that one Flexural modulus of less than 6000 MPa to reduce the flexural modulus of the entire composite can, so that the possibility exists, for example when used as railway sleepers the composites are strong can bend and cause a deviation of a railway track. For the flexural modulus no special upper limit is given. An upper limit the flexural modulus of the surface layer is essentially equal to the value of the surface layer, which is practical can be produced.

In The composite according to claims 1 to 3 amounts to the flexural strength of the surface layer is preferable at least 100 MPa, as in the composite of claim 4, or more preferably 120 MPa. The reason for this is that at a bending strength of less than 100 MPa the possibility that exists when used as thresholds, the long-term flexural strength of composites slightly reduced.

Of the Flexural modulus and flexural strength are determined by JIS Z 2101 prescribed method. The bending stress is on a specimen in a direction to the longitudinal direction of the test piece applied in the vertical direction, wherein the longitudinal direction of the extension direction the long fibers is.

In the composite according to claims 5 to 9 can as the resin for use in the surface layer, the same resins like those used in the composite according to claims 1 to 4 are used.

In the composite according to claim 5 is the average particle size of the filler limited to at least 0.5 mm with the exception of the fibers. The reason for that is, that with an average particle size of the filler less than 0.5 mm when attempting to load the filler with a weight, at least equal to 0.7 times the product of the volume the core layer and the bulk density of the filler is in the mixing process of the filler with the synthetic resin is not achieved sufficient dispersion, so that this Resin does not evenly on the filler can attach and therefore the possibility there is no satisfactory physical properties, such. B. the Bending strength can be achieved. The upper limit of the Particle size of the filler is preferably set so that it is considerably smaller as the thickness of the core layer. If the filler with a diameter is used, which is much larger than the thickness of the core layer, then there is the possibility that this Nail behavior varies so much according to the sites to be nailed, that this Material a permanent Use can not withstand.

In the present invention, the particle size can be obtained by sieving with a standard sieve prescribed by JIS Z 8801. The combination of mesh sizes of typical screens for use in screening is selected from the following:
4.00 mm, 2.80 mm, 2.00 mm, 1.40 mm, 1.00 mm, 850 μm, 500 μm, 300 μm, 212 μm, 106 μm and 75 μm. Other screens with other mesh sizes can be added appropriately.

Of the Value of the particle size of the filler becomes through the mesh basic dimensions of the sieves. The average particle size of the filler is a value that you get by taking the products from the volume ratios in the corresponding Seven remaining fillers to the entire fillers with Exception of fibers and particle size values are summed over all sieves.

Of the filler in the composite according to the invention Although subject to no particular restriction, but to the usable fillers belong for example, amorphous powders, such as. B. rock powder / granules, Glass powder, quartz powder, calcium silicate, ground cement concrete, river sand, Sea sand and quartz sand, powder of inorganic short fibers, such as z. B. wollastonite, inorganic cell-containing powder / granule material, such as B. Expanded Slate, Pumice and foam glass, powdered resins such. B. pulverized Polyvinyl chloride, powdered fiber reinforced resin and powdered fiber reinforced Polyurethane foam, inorganic powder with a relatively small Particle size, like z. Calcium carbonate, fly ash, mica, talc, clay, alumina, Vermiculite and dry sludge powder / granules and previously by Resin bound granules thereof. These fillers can be used individually or in combination used by two or more.

To the usable fibrous fillers belong inorganic fibers, such as. Glass fiber, carbon fiber and boron fiber, and organic short fibers, such as. B. vinylon fiber, polyester fiber, aliphatic polyamide fiber and aromatic polyamide.

In addition, the mentioned above inorganic fillers with a surface treatment by a silane coupling agent can be used. When the polyurethane resin as the resin in the surface layer is used, then preferably a silane coupling agent with a functional group that reacts with an isocyanate group, such as A mercapto group, an amino group and an imino group.

In the composite according to claim 6, the filler used has a particle size distribution curve in which the particle size on the abscissa and a volume ratio of the filler per particle size to all fillers are plotted on the ordinate, two or more peak areas accounting for at least 8% by volume, and also has a size distribution in which the most common particle size values in the smaller peak area of at least 8% by volume are at most 0.7 times the most common particle size values in the larger peak area of at least 8 vol.% Closest to the smaller peak area. The reason for this is that the filler particle of different particle sizes can facilitate the mixing and penetration of the synthetic resin, particularly the thermosetting resin, and can further facilitate an increase in the amount of filler added to substantially improve the lamination effect of the core layer and the surface layer. In addition, the size distribution has peaks at two or more points and, basically, can allow moderate filling of the resin between the fillers. As a result, the composite is elastically compacted during nailing without destroying the core layer, and the elasticity provides improved nail holding ability and durability against the repeatedly attacking nail pulling force.

For the composite according to claim 5 receives one the size distribution curve in the composite according to claim 6 by applying a volume ratio of the filler per particle size to all fillers with the exception of the fibers, in the same way with respect to each Particle size determined becomes. The volume ratio represents a volume ratio between the fillers which are sieved with sieves of adjacent basic dimensions.

Of the Expression "the larger peak area of at least 8% by volume closest to the smaller peak area "shall mean that in the case the presence of a peak area of less than 8% by volume between the large and small peak areas such peak area of less than 8% by volume not than the larger peak area of at least 8% by volume which is closest to the small peak area.

The volume fraction as a percentage of the peak area is obtained as a percentage of an area surrounded by the distribution curve extending between its boundaries where it intersects the abscissa axis and the abscissa, and if the curve does not intersect the abscissa at its boundaries, as a percentage of an area surrounded by the distribution curve extending between minimum points and the abscissa (in the case of using the minimum values, as a percentage of an area of the distribution curve, the abscissa, and vertical lines from the minimum points to the abscissa surrounded), based on a total area bounded by the entire distribution curve and the abscissa, as in 18 shown.

If the peak area has a flat maximum extending parallel to the abscissa, then a center of the parallel part becomes the most frequent particle size value selected.

at the composite according to claim 6 are subject to the fillers, the larger values provide the most common particle sizes, no special restriction. To the fillers belong for example, amorphous granules, such as. B. stone granules, glass granules, Calcium silicate, ground cement concrete, river sand, sea sand and quartz sand, inorganic short fiber powder, such as. B. wollastonite, inorganic cell-containing powder / granules, such as. B. Expanded slate, pumice and foam glass, inorganic powder / granules of relatively small particle size, such as z. Powdered vinyl chloride, powdered fiber reinforced resin, Calcium carbonate and fly ash and dry sludge powder / granules and before Resin bound granules. On the other hand, the fillers are subject to the smaller values of the most common Provide particle sizes, none special restriction. Among the preferred fillers belong for example, powdered quartz sand, quartz, mica, talc, Clay and alumina and as well those resulting in dry-sludge powder / granules and inorganic Powder / granules belong. These fillers can used singly or in combination of two or more. Furthermore, can the ones mentioned above inorganic fillers with surface treatment be used by a silane coupling agent. When the polyurethane resin for the resin in the surface layer is used, then preferably a silane coupling agent with an active Used hydrogen atom which reacts with an isocyanate group, such as A mercapto group, an amino group and an imino group.

In the composite according to claim 9, the polyol equivalent means a value calculated from the following equation (1). The measuring method is as follows. After hydrolyzing the resin, amine derived from the isocyanate component is removed by ion exchange resin, alkaline cleaning and the like so that the polyol component can be recovered, and then the hydroxyl value of the recovered polyol component is measured. Polyol equivalent = molecular weight of KOH × 1000 / hydroxyl number of polyol (mg KOH / g) (1)

When a urethane foam having a polyol equivalent of at least 230 to at most 1500 is used as the thermosetting resin forming the core layer, the density is preferably at least 0.25 g / cm ³ to at most 0.6 g / cm ³ .

On the other hand, if a urethane foam having a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500 is used as the thermosetting resin forming the core layer, then the polyol equivalent is preferably at least 110 to at most 1200.

at a polyol equivalent less than 110, the resin in the core layer may become too hard, So that the possibility exists that the flexibility of the composite itself can become insufficient. on the other hand can at a polyol equivalent of more than 1500 the resin in the core layer become too soft, so the possibility exists that the Nail behavior of the composite can be insufficient.

The Density of the polyurethane resin can be adjusted by adjusting a ratio between the fillers and the resin and foaming of the polyurethane resin between the fillers. The foaming is performed using a propellant. The Propellant can for the resin used to be selected appropriately.

To The usable propellants include, for example, physical Propellant (volatile Propellant), such. Freon, carbon dioxide and pentane, blowing agents of the decomposition type, such as. B. azo compounds and sodium bicarbonate, and blowing agents of the reaction type, such as. B. carbon dioxide, by Reaction of isocyanate and water is generated.

For polyurethane It is preferable to use carbon dioxide obtained by the reaction of Isocyanate and water is generated because Freon can damage the ozone layer. Furthermore the propellant should be previously mixed with the resin.

The Dry sludge powder / granules have a high temperature dry solids content which is generated by a sludge treatment device. The powdered fiber reinforced Resins contain powdered fiber reinforced plastic (FRP) and powdered fiber reinforced Urethane foam. Furthermore, fibrous materials contain needle-shaped or chip-shaped chips, the by fiber-reinforced cockroaches Resin with rectified fibers in the fiber extension direction be generated.

In the composites of claims 10 and 11, the core layer-forming material layers on their pressure side, upon which they are compressed in bending in the thickness direction, are preferably such as to contain fillers having a weight at least equal to 0.7 times the product from the volume of the core layer forming material layers and the bulk density of the filler, so that the fillers in the core layer forming material layers, when compressed, can be brought into contact with each other to provide high elasticity and high strength, while also providing the core layer forming material layers the tensile side are such that they consist of a polyurethane foam having a polyol equivalent of at least 230 to at most 1500 or of a polyurethane foam having a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500 such that she's from the Deflection resulting expansion can yield.

Also included the core layer forming material layers preferably on their Tension side elastic elements, such as. B. rubber chips or springs. The included elastic elements can for vibration damping in provide the composite and thereby the high flexural modulus through the surface layer and the core layer forming material layers on the printing side maintained.

In the composite according to claim 11 can the same layers as the surface layers of the composites according to claims 1 to 9 is used as the core layer forming material layer (hereinafter referred to as "fiber reinforced intermediate layer") be between the core layer forming material layer with filler and synthetic resin (hereinafter referred to as "filler-containing Layer ") and the filler Layer inserted becomes and thermosetting Foam is reinforced by long fibers that are parallel to the longitudinal direction run.

In the composites of claims 10 and 11, the contiguous core layer forming material layers must be bonded together. If these layers are not sufficiently bonded to each other, there is a possibility that an interface at the interface between them caused delamination causes the destruction of the entire composite.

The Although the bonding method is not particularly limited, but belong to the binding process for example, the simultaneous forming of contiguous core layer forming Material layers, the bonding of the molded core layer forming Material layers together using epoxy resin adhesive or urethane adhesive and forming an additional core layer-forming material layer on the formed core layer forming material layer.

The core layer preferably has a compressive shear strength of at least 5 MPa. The reason is the following:
If the compressive shear strength DBa of the core layer is smaller than at least 5 MPa, then flexural strength of the composite corresponding to the material that is only the thermosetting resin reinforced by the longitudinally parallel long fibers as in the surface layer, or the thermosetting resin containing the light fillers and reinforced by the parallel longitudinally extending long fibers. As a result, there is a possibility that bending may cause a shear failure.

Around the compressive shear strength DBa of the core layer of at least 5 MPa To achieve, it is preferable to fill the fillers with silane coupling agent or short fibers, powdered fiber reinforced plastics, powdered fiber reinforced Urethane foam or fibrous fillers to add the needle-shaped or chip form Schnitzel contained by scraping the fiber reinforced resin produced with rectified fibers in the fiber extension direction become.

at Use of an inorganic filler a specific gravity of at least 0.5 is to be preferred. Preferably forms the inorganic filler with a specific gravity of 0.5-1.5 on all fillers 50 vol% or less of the entire core layer.

Further is it in the case of the possible Occurrence of friction shear on the surface to be preferred, at least two longitudinal surfaces of the Core layer of the surface layer surrounded and / or the volume of the core layer at least 50% until at most 65% of the total volume of the composite. The composite thus constructed can be compared to the composite with a surface layer provide improved bending strength from a single material and is also advantageous in terms of a reduction in material costs.

The Manufacturing process is not particularly limited. Of the Composite can be made either by a batch process or produced by a continuous process.

As an indication, an example of the discontinuous production method can be cited, for example, by the Japanese Patent Laid-Open Publication No. Hei 5-138797 is disclosed in which, after forming material for forming the core layer and material for forming the surface layer are preformed and then introduced into molds, a mixture of the long fibers and the thermosetting resin or a mixture of the filler and the thermosetting resin or a molding composition consisting thereof which is to form the surface layer or the core layer is filled in a mold before the preformed material is cured, and then the thermosetting resin is cured by heating.

on the other hand An example of the continuous process is the following. A Number of long fibers to serve as reinforcing fibers is aligned parallel to a given interval while it is to run in one direction. Then a thermosetting foam liquid sprayed from the top of the long fiber group, which are parallel to the direction of movement are aligned. Then you leave the so sprayed on thermosetting Foam liquid penetrate between the fibers, which are the corresponding long fibers form.

Then becomes an extrusion die across from a central part of the long fiber group arranged with the thermosetting Foam liquid waterproof is, and the mixture of the filler and the thermosetting one Resin for forming the core layer is formed so that the core layer is trapped by the long fiber group while being continuously out the extrusion mouthpiece is extruded. Thereafter, the material is continuously a cylindrical mold channel for heat hardening the thermosetting foam liquid supplied in the mold channel, around the core layer and the surface layer at the same time to shape.

When alternative method, the following method is applicable. The Mixture on the filler and the thermosetting one Foam to form the core layer is between the two-ply Supplied to long fiber groups, those with the thermosetting Foam liquid waterproof are, and then through endless ribbons and the like pressed, to be brought into a predetermined cross-sectional shape, the is included by the long fiber group. After that it will be like that shaped layer in the uncured Condition or after foaming continuous to the cylindrical Mold channel supplied and heat-hardened in it. It will then be unchanged or after grinding their surface, z. B. by dry grinding, the cylindrical one Mold channel supplied, So that the thermosetting Foam liquid foamed in the mold channel and heat-cured is to simultaneously or sequentially the core layer and the surface layer to build.

In the composite according to claim 13 are subject to the foam-free thermosetting resin and the low-power Foam used for the intermediate layer are used, no particular limitation, as far as they have the adhesive properties to allow the surface layer and the core layer stick together. As examples, polyurethane resin, Epoxy resin, phenolic resin, unsaturated polyester resin, Urea resin, melamine resin, polyimide resin, polyamide-imide resin, acrylic resin, Natural rubber and synthetic rubber. If necessary, can Catalysts, foam stabilizers, foam auxiliaries, fillers, short reinforcing fibers, dye, Ultraviolet absorbers, Antioxidant, crosslinking agent, stabilizer, Plasticizers, flame retardants, etc. are added (always with Exception of propellants). As an indication should in the case where polyurethane resins for the surface layer and the core layer are used, preferably the same Polyurethane resin can be used to achieve a high adhesion.

at the use of the polyurethane resin also reacts when no Propellant is added, such as. As water, the polyurethane resin with the humidity or moisture from the surface layer or the core layer and develops some foaming, but this degree of foaming is negligible.

Further becomes an intermediate layer between the core layer and the surface layer formed to integrate the core layer and the surface layer. The thickness of the intermediate layer is not particularly limited. If an improvement of the physical properties is desired, such as B. the bending elasticity and the nail pull strength, then the foam-free thermosetting resin or a low density foam with a high modulus of elasticity in greater thickness be formed on the core layer.

In the composite according to claim 14 is the compressive shear strength between the surface layer and the core layer provided intermediate layer on at least Limited to 6.0 MPa when in one of the fiber expansion direction of the Long fibers of the surface layer parallel direction attacks a compressive force on the composite. Preferably, the intermediate layer has a compression shear strength of at least 7.0 MPa, stronger preferably 7.5 MPa. The compressive shear strength can after passing through JIS Z 2102 prescribed shear test method.

Of the reason for the limitation of the shear strength of the intermediate layer with respect to Fiber extension direction of the long fibers of the surface layer to at least 6.0 MPa is the following. With a shear strength the intermediate layer of less than 6 MPa reduces the flex life, which leads to the degradation of the intermediate layer in the form of destruction. The degradation of the interlayer by destruction is spreading from the time of destruction progressing over the destruction area, and the reduction in strength makes rapid progress. As a result For example, this composite can no longer be used for construction material and rail sleepers are used which have high elasticity, flexural strength and fatigue life require.

The Method for providing the shear strength of the intermediate layer of at least 6 MPa is not subject to any particular restriction. To the Example can a method of insertion a high strength and highly elastic resin, such. B. of epoxy resin, between the surface layer and the core layer; a method for increasing the resin density of the intermediate layer at least 1.1 times the resin density of the surface layer and the core layer when the shear strength of the surface layer in terms of the fiber extension direction of the long fibers and the shear strength the core layer is at least 6 MPa; and a method for Arranging a resin-impregnated foil-like Material in the intermediate layer as in the composite of claim 15, given as examples become.

The Method for increasing the resin density between the surface layer and the core layer over the Resin density of the surface layer and close the core layer For example, a method for applying epoxy resin or foamed or unfoamed Urethane resin on the surface the core layer or the intermediate layer, if the multi-layered Material is produced.

In the composite according to claim 15 is the resin impregnated film-like Material a material that is not thermoset with unfoamed Resin or low-power foam is impregnated, and is conveniently for providing the intermediate layer between the core layer and the surface layer used. The resin-impregnated film-like Material is not subject to any particular restriction, as far as it is with non-foamed heat-curable Resin or low-power foam can be impregnated. To the Strength of the intermediate layer itself can increase, a high-strength film-like Material are used.

The resin-impregnated film-like Material is not subject to any particular restriction, as far as it is concerned with liquid urverschäumten thermosetting Resin or foam fluid impregnated of low density can be. To suitable impregnated foil-like Materials belong For example, nonwoven fabric, the inorganic glass fibers or synthetic resin fibers has (for example polyester nonwoven fabric (SUPAN BONDO E 1050, available from Asahi Chemical Industrial Co., Ltd.) and vinylon nonwoven fabric (e.g., BINIRON SUPAN REESU, available from Kuraray Co., Ltd.)) and Tissue. Furthermore can be a porous one Foil with a number of holes made of synthetic resin film, paper and metal fiber fabric.

If the shear strength of the core layer is 6 MPa or the shear strength the surface layer in terms of the fiber extension direction is 6 MPa, then the resin impregnated film-like Allow material that the Compressive shear strength of the intermediate layer with respect to the direction parallel to Fiber expansion direction is at least 6 MPa, by the resin density between the surface layer and the resin-impregnated film-like Material and the resin density between the core layer and the resin impregnated film-like Material to at least 1.1 times the resin density of the core layer and the surface layer be set.

If Polyurethane resin as the resin of the core layer and the surface layer is used and the intermediate layer between the core layer and the surface layer added then it can be resin impregnated film-like Material whose raw material has a chemical / physical affinity to the resin the core layer and the surface layer has, such. As vinylon fiber or glass fiber with silane adhesive treated and has excellent adhesive properties, allow that the Resin density between the surface layer and the foil-like one Material and resin density between the core layer and the film-like Material at least equal to 1.05 times the resin density of the core layer and the surface layer is, for. B. if the shear strength of the core layer 6 MPa or Shear strength of the surface layer 6 MPa re the fiber extension direction is.

In the composites according to claims 1 to 7 and the claims 9 to 15 is used as the resin of the core layer and as the resin surface layer preferably used polyurethane foam, as well as in the Composite according to claim 16th

Of the reason for the use of polyurethane foam for the core layer is that he has a has relatively high mechanical strength and easy to foam Closed cells can form and an excellent low absorption capacity having.

To Commonly available polyurethane foams include known ones Polyurethane foams obtained by reaction with polyol and polyisocyanate receives.

The polyols which have at least two hydroxyl groups at their molecular end include, for example, polyether polyol, such as. Example, polypropylene oxide, polyethylene oxide and polytetramethylene glycol and copolymers thereof, polyester polyols, such as. Example, polycondensate of aliphatic dicarboxylic acid, such as adipic acid, and glycol having not more than 12 carbon atoms, such as. Ethylene glycol, propylene glycol, butylene glycol and hexamethylene glycol, polyester polyol which is a polycondensate of hydroxycarboxylic acid, such as e.g. Poly-ε-caprolactone and a copolymer thereof, as well as polymer polyols which are graft copolymers of the polyols and a polymer of a monomer having a vinyl group. These may be used singly or in combination of two or more. The useful polyisocyanates have at least two isocyanate groups, and include, for example, hydrogenated materials of 4,4'-methylene diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and 4,4'-methylenediphenyl diisocyanate, polynuclear compounds thereof, and polynuclear compounds of their isomers. These may be used singly or in combination of two or more compounds. In view of safety, reactivity and convenience, a mixture of 4,4'-methylenediphenyl diisocyanate and a polynuclear compound of its isomer (hereinafter referred to as "polymeric MDI") is preferable.

Examples blowing agents used in the reaction are thermal decomposable blowing agents, gas propellants, such. Freon, and water. Furthermore, can By-products are used, such as. As decomposed gas, the at the reaction of the thermally decomposable blowing agent is generated. Since Freon can degrade the ozone layer, preferably carbon dioxide should be used by the reaction of isocyanate and water arises. Furthermore the propellant should be previously mixed with the resin.

If necessary, can the urethane foam catalysts, foam stabilizers, foam auxiliaries, fillers, short reinforcing fibers, dye, Ultraviolet absorber, antioxidant, crosslinking agent, Stabilizers, plasticizers, flame retardants, etc. added become.

The Although catalysts are not particularly limited, but for example Organotin catalysts such as dibutyltin dilaurate, amine catalysts and temperature-sensitive catalysts are used.

The Composite materials according to claims 13 to 16 can either by a batch process or by a continuous process can be generated.

Preferably should the cure time the respective layers as possible be exactly coordinated. The reason for this is apparently that by doing so an increased Binding force can be provided to help improve Interfacial strength contribute when chemical bonds between corresponding layers be formed.

When Reference is made to the discontinuous preparation. To the Example is material for forming the core layer and material for the formation of the surface layer first preformed and then in molds brought in. In this process, the resin impregnated film-like Material previously impregnated with foam-free thermosetting resin, on a surface of the thus-used preformed material on the side of the material placed on top of the core layer and the surface layer be laminated. Before curing the preformed material is the mixture of long fibers and synthetic resin foam, that the surface layer form, or the mixture of filler and synthetic resin, the the core layer is to form, or another preformed material, that the surface layer or form the core layer, filled in a mold, and then the resin of the core layer and the surface layer become and the unfoamed thermosetting Hardened resin by heating.

at a continuous process z. B. a number of long fibers, as reinforcing fibers should be aligned parallel to a given interval, while they move in two vertical planes in one direction. Then a polyurethane foam fluid over the Long fiber groups sprayed, which are parallel on the locomotion track in two vertical planes were aligned so that the sprayed Polyurethane foam liquid penetrates between the fibers, which are the corresponding long fibers form.

Further is in the state in which the resin-impregnated foil-like Material previously with foam-free thermosetting resin liquid or low-power foam fluid was soaked between The two-layered long fiber groups is arranged with the liquid thermosetting Foam impregnated are, the mixture of the filler and the thermosetting one Foam for forming the core layer between endless bands and The like introduced and formed by them, so that they to a predetermined cross-sectional shape are formed by the long fiber group is enclosed, and then continuously in the uncured state supplied become. Thereafter, they continuously become a cylindrical molding channel supplied So that the thermosetting foam liquid foamed in the mold channel and heat-cured can be at the same time the core layer, the surface layer and to form the intermediate layer.

The composite of claim 17 has a total thickness of at least 100 mm, and the thickness ratio of the core layer to the total thickness of the surface layers covering the core layer in the thickness direction is in the range of 9/1 to 1/1. The reason for this condition is that in a behavior On the other hand, if the ratio is less than 1/1, there is a possibility that either the compressive strength or the nail holding ability resulting from the filler addition may not be satisfactory.

In the composite according to claim 18, the core layer has at least two core layer-forming composition layers (A) with filler and synthetic resin and at least one core layer-forming composition layer (B) reinforced with long fibers thermosetting Resin between the two core layer-forming compositions (A), (A) the core layer forming composition layers (A) added is and parallel to it in the longitudinal direction of the composite runs, and a relationship between the total thickness of the core layer forming composition layer (A) and the total thickness of the core layer forming composition layer (B) is in the range of 95/5 to 50/50. The reason for this condition is that at a relationship greater than 95/5 the nail retention of the core layer forming composition layer (B) which fiber reinforced Interlayer is reduced, while on the other hand at a relationship less than 50/50 the possibility that exists the compressive elastic limit reduced.

In the composite according to claim 19 becomes the surface layer laminated on the core layer so that it has at least two surfaces of Core layer covered with respect to the thickness direction; the composite has a total thickness of at least 100 mm in its thickness direction, and the thickness of the surface layer on the side of the composite where a tensile force is acting, when the composite is bent in the thickness direction, at least 5% to at most 20% of the total thickness, and the thickness of the surface layer on the side of Composite, which acts on a compressive force, is at least 1.5% to at most 15% of the total thickness. The reason is the following.

If the thickness of the surface layer on the side where a tensile force attacks, is too small, can not be sufficient Bending strength can be achieved. On the other hand, if the thickness of the surface layer on the side of the composite where the tensile force acts is too large, then The effect of a reduction in material costs can come from the provision of the core layer results, reduce. If the thickness of the surface layer on the side of the composite where a compressive force is acting, is too small, then the core layer bulged by deformation become, whereby no sufficient bending strength is achieved. On the other hand, if the thickness of the surface layer on the side of the Composite, where the pressure force attacks, is too large, then The effect of a reduction in material costs can come from the provision of the core layer results, reduce.

In the composite according to claim 20 surrounds the surface layer four surfaces the core layer and forms at least 10 vol .-% to at most 65 vol% of the total composite. The reason for this Condition is that at less than 10% by volume, the bending strength becomes insufficient while, on the other hand, at more than 65% by volume the possibility exists that either the compressive strength or the addition of the fillers resulting nail retention in certain circumstances is not satisfactory.

Of the Composite according to the invention is suitable as a building material. He can be suitable as a substitute for wood and also foreseen Uses for weight reduction of concrete products used be such. As of lids, in a water treatment plant used pressure-absorbing plates in dirty water or used in appropriate places, shuttering for use in the Shield Earth Retaining Wall method (shield tunneling method; hereinafter referred to as "SEW construction method"), and Rail sleepers as recited in claim 21.

To note that the SEW construction method is a construction method in which a wall of high Strength and high durability built into a Erdstützwand as part of it through which a shield tunneling machine passes so that the shield tunneling machine can pierce directly this part of the wall to him from a starting point to pass through to an end point, without the wall circular through People or machines must be cut out.

at the composite material and the rail sleeper according to the present invention can the surface layer and the core layer on their exposed sides when needed with a decorative layer, a weatherproof layer and a waterproof layer are provided.

The Although weatherproof layer is not subject to any particular restriction, but as an example, a coating layer can be given as a weatherproof layer, which is formed by applying a weatherproof paint.

The Although the waterproof layer is not particularly limited, it can but made of a waterproof film and a waterproof plate are made of rubber, synthetic resin, sheet metal or one Combination thereof, as well as from a coating layer by applying a non-underwater paint and a corresponding coating, by applying or impregnating with water-repellent, oil-containing Material, such. As paraffin or petrolatum is formed.

Of the Composite according to the invention Although has an excellent nail-holding ability, but the nail-holding ability can by forming prepared holes at nailing sites, pour in from adhesive into the prepared holes and then knocking the nail in the holes will be further improved.

The Invention will be described below only by way of examples Reference to the attached Drawings described. Showing:

1 a first embodiment of a composite according to the present invention, which is a longitudinal section of the composite;

2 a change curve of the bending stress of the composite according to 1 ;

3 a schematic diagram showing schematically a production unit for the composite according to 1 represents;

4 a schematic drawing of an enlarged sectional view of a core layer of the composite according to 1 ;

5 a second embodiment of the composite according to the invention, which is a longitudinal section of the composite;

6 a third embodiment of the composite according to the invention, which is a longitudinal section of the composite;

7 a fourth embodiment of the composite according to the invention, which is a longitudinal section of the composite;

8th a fifth embodiment of the composite according to the invention, which is a longitudinal section of the composite;

9 a sixth embodiment of the composite according to the invention, which is a longitudinal section of the composite;

10 a seventh embodiment of the composite according to the invention, which schematically illustrates a perspective view of the composite;

11 a diagram for explaining a development mechanism of the bending strength of the composite;

12 a perspective view of an eighth embodiment of the composite according to the invention;

13 a diagram schematically showing a vertical production line for use in the production of the composite according to 12 represents;

14 a sectional view of the composite shown in Reference Example 1;

15 a sectional view of the composite prepared in Reference Example 2;

16 a representation for explaining the method of a shear test;

17 a schematic drawing of an enlarged sectional view of a core layer of a conventional composite material; and

18 Fig. 10 is a diagram for explaining the determination method of the volume fraction of a peak area from a particle size distribution curve of the filler.

BEST MODE FOR CARRYING OUT THE INVENTION

The detailed Description of the embodiments The present invention will be described with reference to the accompanying drawings where.

In 1 The first embodiment of a composite according to the present invention is shown.

As in 1 shown, the composite exhibits 1a a core layer 2a and a surface layer 3a on.

The core layer 2a has filler 22 and thermosetting resin containing a filler 22 , whose weight is at least equal to 0.7 times the product of the volume of the core layer and the bulk density of the filler, and has a density of at least 0.3 g / cm ³ to at most 2.3 g / cm ³ .

The filler 22 It consists of at least one powder / granules selected from the group consisting of inorganic powder / granules, dry sludge powder / granules and pulverized fiber reinforced resin.

As in 2 shown, obtained when applying the bending stress of the core layer 2a which varies with the change of the deflection, a change curve having a singular point P in which the slope of the tangent T, which gradually decreases from the start time of the bend, increases again before becoming negative. The core layer 2a has a deflection of at most 0.8% at the singular point P, and incidentally has a flexural modulus of at least 800 MPa when it is further deflected by the deflection at the singular point P on.

The surface layer 3a is arranged so that it is the core layer 2a surrounded by the outside and with the core layer 2a is integrated and consists of thermosetting foam whose long fibers 5 are aligned generally parallel to the longitudinal direction.

The surface layer 3a forms at least 10% by volume to at most 65% by volume of the total volume.

Next, a detailed description of the manufacturing process of the composite will be given 1a using an in 3 given production unit.

As in 3 shown, instructs the production unit 4 a discharge device 41 , an impregnating device 42 , a continuous mixer 43 , a molded mouthpiece 44 , a molding channel 45 and a sampling device 46 on.

The discharge device 41 is engineered to provide continuous thermosetting foam fluid 59 which is produced by mixing raw material supplied from a raw material container (not shown) and the liquid to the long fibers 55 sprayed when passing through the molding channel 45 be directed in parallel and continuously to the side of the sampling device 46 be taken out.

The impregnating device 42 is with an impregnation plate 42a and an impregnation pad (not shown) for receiving the impregnation plate 42a fitted. The long fiber group 55 to which the thermosetting foam fluid 59 is sprayed between the impregnation pad and the impregnation plate 42a Kneaded so that the thermosetting foam liquid 59 can penetrate evenly between the fibers.

The continuous kneading machine 43 is designed to contain the thermosetting foam liquid to form the core layer 2a and the filler mixed to thereby produce a raw material mixture, and further, the raw material mixture is continuously fed to the die mouthpiece 44 supplies.

The molded mouthpiece 44 is designed to be that of the continuous kneading machine 43 to Guided raw material mixture continuously brings in a predetermined shape and also the molded material on the way between the impregnator 42 and the molding channel 45 as a molded material 58 for use in forming the core layer, a middle portion of the long fiber group 55 supplies.

The mold channel 45 is made by combining four endless bands 45a formed (only two of which are shown in the drawing), which are driven by drive means for rotation in the same direction, and has a rectangular cross-sectional shape. He also has a - but not shown - heating device to the heat-curable foam liquid 59 with which the long fibers 5 are impregnated, the mold channel 45 be supplied continuously, and the thermosetting foam liquid in the molded material 58 to foam and harden, thereby forming the composite 1a with the core layer 2a and the surface layer 3a to create an in 1 has shown cross-sectional shape. The composite produced in this way is continuously transported through the molding channel.

The removal device 46 is designed to be the composite material 1a withdraws at a steady rate.

In the composite produced in this way 1a becomes the surface layer 3a formed in a state in which the long fibers 5 are aligned parallel to the longitudinal direction of the thermosetting resin. Therefore, the composite is easy to nail and the like, and also has excellent longitudinal bending strength.

In addition, because the core layer 2a the filler 22 and the thermosetting resin, and since they are the filler 22 having a weight which is at least equal to 0.7 times the product of the volume of the core layer below the bulk density of the filler, and having a density of at least 0.3 g / cm ³ to at most 2.3 g / cm ³ has, the fillers 22 in the state in which they are brought into contact with each other, bonded by the thermosetting resin, as in 4 shown.

Therefore, the core layer indicates 2a under compression a slight deformation, which also from the surface layer 3a so that under compression it never exceeds the proportional limit of the surface layer 3a below. Accordingly, the composite as a whole has excellent compressive strength and also has the filler 22 the core layer 2a an improved nail-pulling behavior. In other words, because the filler 22 is tightly packed, the resistance to nail pulling through the filler 22 and the thermosetting resin 21 increases, and therefore the nail pull strength improves.

As inorganic powder / granules, dry sludge powder / granules and pulverized fiber reinforced resin as filler 22 Further, the coefficient of thermal expansion of the filler is about 1/10 of the coefficient of the thermosetting resin. As a result, the thermal expansion coefficient of the core layer comes 2a that of the glass fiber reinforced surface layer 3a Near. As a result, little deformation at the interface between the surface layer and the core layer occurs even with a large change in the ambient temperature, whereby the long-term adhesion properties between the layers become very reliable.

Furthermore, since the surface layer 3a comprises a thermosetting foam reinforced by the longitudinally longitudinally aligned long fibers and forming at least 10% by volume to at most 65% by volume of the total volume, the composite has sufficient flexural strength and also exhibits cracking or breaking resistance during nailing ,

In addition, the change curve of the bending stress of the core layer 2a the singular point P in which the slope of the tangent gradually decreasing from the start time of the victory increases again before becoming negative, and moreover, the deflection of the core layer in the singular point P is at most 0.8%. Further, upon further deflection beyond the value in the singular point, the core layer has a flexural modulus of at least 800 MPa. As a result, the bending strength is improved. The appearance of the singular point provides the result that upon flexing or compression of the composite, the fillers are brought into full contact with one another to produce improved strength.

5 shows the second embodiment of the composite according to the invention.

As in 5 shown, is the composite 1b with a core layer 2 B Shaped between the surface layers 3b is inserted at the top and bottom of the core layer.

The core layer 2 B It consists of filler contained in a proportion of more than 50% by volume up to a maximum of 95% by volume and polyurethane foam with a polyol equivalent of not less than 230 up to 1500, or polyurethane foam with a density of not less than 0.3 g / cm ³ and a polyol equivalent of at most 1500.

The surface layers 3b are made of thermosetting foam, which is reinforced by long fibers, which are aligned parallel in the longitudinal direction.

The composite 1b is prepared by the following processes: First, a mixture of the filler and the polyurethane foam liquid is filled in a mold to bring the mixture into the form of a core layer. Then, before the cured material is cured, the molded material is placed between a thermosetting foam sheet reinforced by fibers which become the surface layer, and then cured by heating in the casting mold in this state.

Because in this composite 1b as mentioned above, the core layer 2 B the fillers contained in a proportion of more than 50 vol .-% to at most 95 vol .-%, in the state in which the fillers are brought into contact with each other, the fillers 22 bonded together by the polyurethane foam, as well as in the case of the above-mentioned composite material 1a ,

Therefore, the core layer indicates 2 B under pressure, a slight deformation, which also from the surface layer 3b dependent, so that they never under compression the proportional limit of the surface layer 3b below. Accordingly, the composite as a whole has excellent compressive strength, and further, the nail pulling performance by the filler of the core layer becomes 2 B improved. In other words, because the filler 22 densely packed, the resistance against nail pulling is increased by the filler and the polyurethane foam, and therefore, the nail pulling strength is increased.

In addition, because the polyurethane foam, which is the core layer 2 B forms a polyol equivalent of at least 230 to at most 1500 or a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500, also improves the flexibility.

at Use as a rail tie and the like is the composite therefore easily able to reduce noise vibrations to steam. There as well the core layer resistant against destruction is when a damage caused by wear, will damage then on the surface layer caused and thus easily recognizable.

Further The relative density of the produced composite can be easily determined by Regulate the relative density of fillers of the core layer adjusted so that the Composite for Various applications can be used, ranging from the mass-saving Application to the mass-loaded application range.

In 6 the third embodiment of the composite according to the invention is shown.

As in 6 shown, the composite exhibits 1c a core layer 2c with two filler layers 23 . 24 as core layer forming compositions and a surface layer 3c which is arranged to be the core layer 2c surrounds.

The filler-containing layers 23 . 24 consist of polyurethane foam having a polyol equivalent of at least 230 to at most 1500 or of polyurethane foam having a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500 and of material having a filler having a weight at least equal to 0.7 times the product of the volume of the filler-containing layers 23 . 24 and the bulk density of the filler.

The two filler layers 23 . 24 differ in the mixing ratio of the fillers from each other, have slightly different physical properties and are glued together at the interface therebetween.

The surface layer 3c consists of thermosetting foam reinforced by the longitudinally paralleled long fibers.

Because in the composite 1c the core layer 2c from two filler-containing layers 23 . 24 With different physical properties, as mentioned above, the filler-containing layers act 23 . 24 and the surface layer 3c efficiently against bending together to provide improved strength and flexibility of the composite.

In 7 the fourth embodiment of the composite according to the invention is shown.

As in 7 shown is the composite 1d with the above-mentioned composite 1c identical, except that a core layer 2d from two filler-containing layers 23 . 24 with different physical properties and a fiber-reinforced interlayer 25 consists.

The fiber reinforced intermediate layer 25 consists of thermosetting foam reinforced by longitudinally parallel longitudinal fibers, as in the case of the surface layer 3c the case is, and is with the upper and lower filler layers 23 . 24 glued so that it is integrated with these.

Because in this composite 1d the fiber reinforced interlayer 25 between the filler-containing layer 23 and the filler-containing layer 24 is provided, as mentioned above, the hammered nail through the long fibers of the fiber-reinforced intermediate layer 25 bonded to provide improved nail retention of the composite.

Therefore the composite can be suitably used for a rail tie (especially a railway sleeper), a pressure-absorbing plate and the shield Earth Retaining Wall (SEW) method be used, which has a high flexural strength and a high Require bending modulus. Because the product size for purposes that do not have high bending strength and require a high flexural modulus, can be downsized, can be achieve a material cost savings.

In 8th shows the fifth embodiment of the composite according to the invention.

As in 8th shown is the composite 1e identical to the above-mentioned composite 1d , except that a core layer 2e of two identical filler-containing layers 23 . 23 and a fiber-reinforced intermediate layer 25 consists.

In 9 shows the sixth embodiment of the composite according to the invention.

As in 9 shown is the composite 1f with the above-mentioned composites 1d . 1e identical, except that a core layer 2f from three filler-containing layers 23 . 24 . 26 with different physical properties and a fiber-reinforced interlayer 25 consists.

Specifically, the fiber-reinforced interlayer 25 is between the filler-containing layer 24 and the filler-containing layer 26 provided, and the filler-containing layer 23 and the filler-containing layer 24 are glued directly to each other.

In 10 shows the seventh embodiment of the composite according to the invention.

As in 10 shown, the composite exhibits 1g a core layer 2g containing synthetic resin as a main component and a surface layer 3g comprising thermosetting foam reinforced by long fibers which are directed parallel in the longitudinal direction, or elastic synthetic resin reinforced by long fibers directed parallel in the longitudinal direction and arranged to form the core layer 2g surrounds.

The core layer 2g and the surface layer 3g have a relationship satisfying the inequalities CSa ≥ 1/2 × CSb, Ea <Eb, and ESa ≥ 1/2 × ESb (where Ca is a compressive elastic modulus of the core layer in the longitudinal direction; Cb is a compressive elastic modulus of the surface layer in the longitudinal direction; CSa is the yield strain Ea a tensile modulus of elasticity of the surface layer; ESa the flow elongation under tension of the core layer and ESb the flow elongation under tension of the surface layer), and from the equations it follows that 300 MPa ≦ Ca ≦ 12000 MPa, 0.005 ≦ CSa, 50 MPa ≦ Ea, 0.005 ≦ ESa, 2000 MPa ≦ Cb ≦ 8000 MPa, 0.01 ≦ CSb, 5000 MPa ≦ Eb ≦ 18000 MPa and 0.01 ≦ ESb.

The core layer 2g contains the filler with a weight that is at least equal to 0.7 times the Product of the volume of the core layer and the bulk density of the filler, and has a shearing strength DBa of at least 5 MPa.

The composite created in this way 1g provides the results that it suppresses destruction of the core layer and improves flexibility in addition to the bending strength, the limit of proportionality under pressure, the nail behavior and nail pulling behavior. Therefore, when the composite is used as a rail tie and the like, it easily causes vibration damping for noise reduction.

In 12 shows the eighth embodiment of a composite according to the invention.

As in 12 shown, the composite exhibits 1h a core layer 2h , an intermediate layer 7h and a surface layer 3h on and has a rectangular cross-sectional shape.

The core layer 2h comprises filler and polyurethane foam, containing the filler having a weight at least equal to 0.7 times the product of the volume of the core layer and the bulk density of the filler and having a density of at least 0.3 g / cm ³ to at most 2.3 g / cm ³ .

Of the filler consists of at least one powder / granules that is from the group selected is that of inorganic powder / granules, dry sludge powder / granules and pulverized fiber reinforced resin consists.

The surface layer 3h is made of polyurethane foam whose long fibers are oriented generally parallel in the longitudinal direction.

The surface layer 3h forms at least 10% by volume to at most 65% by volume of the total volume.

The intermediate layer 7h consists of polyurethane resin in the form of non-foamed thermosetting resin. The surface layer 3h and the core layer 2h are about the interlayer 7h integrated by an adhesive connection.

The intermediate layer 7h has a resin-impregnated sheet-like material, although not shown, and has a shear strength of at least 6 MPa when oriented in a direction parallel to the fiber extension direction of the long fibers 5 the surface layer 3h is compressed.

In 13 is a vertical forming line according to an example of the manufacturing method of the composite 1h shown.

Based on 13 the production process will be described according to the corresponding subsequent processes.

(1) Feeder and parallel alignment of long fibers:

In 13 become long fibers 81 supplied from straightening blades (not shown) from four directions corresponding to the respective sides of the obtained product (only two directions are shown in the diagram) so that long fiber bundles 82 which are pulled under tension and thereby aligned generally parallel to given distances are conveyed in one direction.

(2) Impregnate, Position and Introduce of fiber strands:

Thereafter, polyurethane foam is allowed in the form of a solution of polyurethane foam containers 83 above the moving long fiber bundles 82 are arranged on the long fiber bundles 82 seep to cling to it. Then the long fiber bundles 82 with the polyurethane foam impregnated thereon 84 fed. The impregnation plates 84 are moved back and forth in a direction perpendicular to the direction of movement of the long fiber bundles to the long fiber bundles 82 to knead and to let the polyurethane foam penetrate between the long fibers, which are the long fiber bundles 82 form.

Then the resin impregnated long fiber bundles 85 , which correspond in their position to the four sides, on their respective sides in inlets of movable forms 86 arranged.

Then can guides (not shown) used to make a change or fine adjustment to execute the direction of movement.

Then the resin impregnated long fiber bundles 85 in each case by one of a removal device 88 attacking upload into one of the moving forms 86 introduced and come into contact with four sides of the movable mold 86 , It should be noted that the movable shape 86 defines a closed space in which endless ribbons 86a arranged in four directions (only two directions are shown in the diagram).

(3) Inserting the resin impregnated film-like Materials:

First, unfoamed thermosetting resin liquid is allowed to flow out of a mixing head 89 on resin-impregnated film-like material 87 and then let the resin-impregnated film-like material 87 by impregnating rollers 90 run to the film-like material 87 with the unfoamed thermosetting resin to impregnate. The impregnated in this way resin-impregnated film-like material 87 ' becomes a movable form 86 introduced so that it in the produced composite 1h between the core layer 2h and the surface layer 3h can be arranged.

(4) pouring filler:

Then a polyurethane foam composition 92 , the quartz sand is added and mixed therein, poured and from a mixing device 91 delivered into a room, that of the long fiber bundles 85 on the four sides inside the movable mold 86 and impregnated with the polyurethane resin liquid, and the resin-impregnated film-like material 87 surrounded on the inside of the long fiber bundles 85 arranged and impregnated with the unfoamed thermosetting resin. The mixing device 91 is with an inlet 91a for the polyurethane foam fluid, an inlet 91b for the filler and a main body (a mixing section).

(5) Forming the laminate:

The resin liquid containing the above-mentioned filler, the long fiber bundles impregnated with the surrounding resin liquid 85 and the resin-impregnated film-like material 87 ' , which is impregnated with the unfoamed thermosetting resin, such. As with non-foamed polyurethane resin, are by the endless belts 86a which the moving form 86 form, at the same time transported downwards.

In the course of the movement, the filler-containing resin becomes the long-fiber bundle impregnated with the surrounding resin liquid 85 and the resin impregnated film-like material impregnated with the unfoamed thermosetting resin 87 first of which by a heating / cooling section 86c heated endless ribbons 86 heated to develop a foaming and curing reaction and thereby a fiber-reinforced resin laminate 1h ' in which the core layer 2h , the surface layer 3h and the intermediate layer introduced therebetween 7h generally shaped. Then the fiber reinforced resin laminate 1h ' through the endless ribbons 86a cooled by a lower heating / cooling section 86c be cooled.

(6) cooling:

Then the multi-layered structure becomes the movable mold 86 taken and a cooling device 93 fed. The multilayer structure is by chill rolls 93a in the cooling device 93 completely cooled.

(7) cutting:

After passing through the sampling device 88 becomes the fiber reinforced resin laminate with a cutter 94 cut to a desired length to the composite 1h to obtain.

In this composite 1h are the surface layer 3h and the core layer 2h over the intermediate layer 7h integrated by gluing, as mentioned above. Therefore, this composite can be easily nailed and has excellent bending strength in the longitudinal direction as well as in the case of the composite 1a , and may also be suitably used as a building material, for example in a SEW construction waterproofing / access shield wall shield shield.

Similar to the composite z. B. by the Japanese Patent Laid-Open Publication No. Hei 5-138797 in which the thermosetting foam surface layers in which long reinforcing fibers which are longitudinally aligned in parallel and generally distributed in parallel are laminated to surfaces of the core layer comprising the thermosetting foam having filler added, the composite can relatively easily become large Thickness can be produced. However, since both the core layer and the surface layer have the thermosetting foam, the interfacial strength for application to the SEW construction method is so low that peeling is liable to be generated at the interface and, therefore, the use of the composite was for it Construction method practically difficult.

In contrast, in the composite 1h the surface layer 3h and the core layer 2h over the intermediate layer 7h firmly bonded together by bonding, so that the problem of detachment caused at the interface is prevented. In other words, since the urbed thermosetting resin layer is present at the interface between the core layer and the surface layer, the composite at the interface has excellent adhesive strength or, in other words, excellent interfacial strength.

This is probably due to the fact that the adhesion at the interface, in other words, the chemical bond per unit area and the degree of anchoring in the interface, are higher as the corresponding values at the interface of the bound together unfoamed Layers.

By the way, the intermediate layer points 7h a shear strength of at least 6 MPa when in a direction parallel to the fiber extension direction of the long fibers 81 the surface layer 3h is compressed, so that when the composite is subjected to a bending test, the core layer or the surface layer breaks rather than the intermediate layer. Therefore, fracture propagation across the fracture surface is prevented, causing a sudden reduction in strength occurring upon fracture of the intermediate layer. Accordingly, the composite of the present invention may preferably be used for purposes requiring high elasticity, high flexural strength, and durability in long-term bending stress, including construction materials such as rubber. As the removal / access sealing wall for shield tunneling for use in the SEW process, and rail sleepers.

The composite according to the invention is not limited to the embodiments explained above. For example, while the production unit 4 of the embodiment set forth above so that the thermosetting foam liquid 59 about the long fiber group 55 sprayed and then through the impregnator 42 is impregnated with the liquid, but the long fiber group 55 Alternatively, it may be immersed in the thermosetting foam fluid or passed through two rollers with beads to be impregnated with the thermosetting foam fluid.

In addition, while in the manufacturing process of the composite 1h the vertical production unit is used, but alternatively a horizontal production unit may be used.

EXAMPLES

below Examples of the present invention will be described in more detail.

(EXAMPLE 1)

To Production of a Core Layer with a Cross Section Size of 190 × 100 mm, the one thermosetting Urethane foam liquid and the filler shown in Table 1 below The core layer was poured in the mold to form a composite with a cross-sectional size of 200 × 140 mm to produce a surface layer with the long fibers and thermosetting given in Table 1 foam liquid and extended along the four longitudinal surfaces.

Of the produced composite showed that a ratio of the core layer thickness to the total thickness of the surface layer covering the core layer in the thickness direction was 2.5; that the thickness of the surface layer on the side of the material, on when bending the composite in the thickness direction, a tensile force was applied, 14% of the total thickness amounted to; and that the Thickness of the surface layer on the side of the material on which a compressive force was exerted 14% of the total thickness was.

In Table 1, the polyether polyol is a polyether polyol with propylene oxide addition (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 1703, hydroxyl value 380, polyol equivalent 147), and the maximum particle diameter fraction represents a fraction of the most common particle diameter values in adjacent peak areas of at least 8% by volume.

The particle diameter of the filler was regulated with a sieve as shown in Table 1. The content of the filler was obtained by dividing the filler weight in the core layer by (volume of the core layer × bulk density of the filler). The densities in the table below are expressed in units of g / cm ³ .

[Table 1]

(EXAMPLE 2)

To Preparation of a core layer with a cross-sectional size of 190 × 160 mm, which the thermosetting Urethane foam liquid and the filler shown in Table 2 below The core layer was poured in the mold to form a composite with a cross-sectional size of 200 × 200 mm to produce a surface layer with the long fibers and thermosetting given in Table 1 foam liquid had, which extended along the four longitudinal surfaces.

Of the produced composite showed that a ratio of the core layer thickness to the total thickness of the surface layer covering the core layer in the thickness direction was 4; that the Thickness of the surface layer on the side of the material, when bending the composite in the thickness direction, a tensile force was applied, 10% of the total thickness amounted to; and that the Thickness of the surface layer on the side of the material to which a compressive force has been exerted 10% of the total thickness was.

In Table 2 sets the polyether polyol a polyether polyol with propylene oxide additive (available from Mitsui Chemicals, Inc., MN-3050S, hydroxyl number 56, polyol equivalent 1000), and the maximum particle diameter fraction represents a proportion the most common Particle diameter values in adjacent peak areas of at least 8% by volume represents.

Of the Particle diameter of the filler was regulated with a sieve as shown in Table 2.

[Table 2]

(EXAMPLE 3)

To Preparation of a core layer with a cross-sectional size of 190 × 80 mm, which the thermosetting Urethane foam liquid and the filler shown in Table 3 below The core layer was poured in the mold to form a composite with a cross-sectional size of 200 × 120 mm to produce a surface layer with the long fibers and the thermosetting materials shown in Table 3 foam liquid had, which extended along four longitudinal surfaces.

Of the produced composite showed that a ratio of the core layer thickness to the total thickness of the surface layer covering the core layer in the surface direction in the thickness direction was 2; that the Thickness of the surface layer on the side of the material, when bending the composite in the thickness direction, a tensile force was applied, 21% of the total thickness amounted to; and that the Thickness of the surface layer the side of the material to which a compressive force has been applied 13% of the total thickness was.

In Table 3 sets the polyether polyol as a mixture with a polyol equivalent of 270 by mixing 50% by weight of polyether polyol with propylene oxide additive (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 1703, hydroxyl number 380), and 50% by weight of polyether polyol with propylene oxide additive (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 3900, hydroxyl number 35).

Of the Particle diameter of the filler was regulated with a sieve as shown in Table 3.

[Table 3]

(EXAMPLE 4)

After producing a core layer with a cross-sectional size of 190 × 100 mm, which heat thermosetting foam resin and the filler shown in Table 4 below, the core layer was cast in the mold to produce a composite having a cross-sectional size of 200 × 140 mm having a surface layer with the long fibers and the thermosetting foam liquid shown in Table 4 had, which extended along four longitudinal surfaces.

Of the produced composite showed that a ratio of the core layer thickness to the total thickness of the surface layer covering the core layer in the thickness direction was 2.5; that the thickness of the surface layer on the side of the material, when bending the composite in the thickness direction, a tensile force was applied, 14% of the total thickness amounted to; and that the Thickness of the surface layer on the side of the material to which a compressive force has been exerted 14% of the total thickness was.

In Table 4 sets the polyether polyol as a mixture with a polyol equivalent of 270 by mixing 50% by weight of polyether polyol with propylene oxide additive (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 1703, hydroxyl number 380) and 50 wt .-% polyether polyol with Propylene oxide additive (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 3900, hydroxyl number 35).

Of the Particle diameter of the filler was regulated with a sieve as shown in Table 4.

[Table 4]

(EXAMPLE 5)

After this a polyethylene terephthalate resin powder and that in the following Table 5 specified filler were mixed and dispersed, the mixture was used to a core layer having a cross-sectional size of 200 × 100 mm by hot pressing manufacture. Thereafter, the core layer was poured in the mold, to produce a composite having a cross-sectional size of 200 × 140 mm, the a surface layer with long fibers, liquid unsaturated Polyester resin of the iso series and fly ash hollow spheres (available from Japan Fillite Ltd.), as shown in Table 5, the extends along two upper and lower surfaces.

Of the produced composite showed that a ratio of the core layer thickness to the total thickness of the surface layer covering the core layer in the thickness direction was 2.5; that the thickness of the surface layer on the side of the material, when bending the composite in the thickness direction, a tensile force was applied, 14% of the total thickness amounted to; and that the Thickness of the surface layer on the side of the material to which a compressive force has been exerted 14% of the total thickness was.

Of the Particle diameter of the filler was regulated with a sieve as shown in Table 5.

[Table 5]

COMPARATIVE EXAMPLE 1

apart that the Core layer and the surface layer as shown formed in Table 6 below became the composite in the same manner as in Example 1 produces.

[Table 6]

(COMPARATIVE EXAMPLE 2)

apart that the Core layer and the surface layer as shown formed in Table 7 below became the composite in the same manner as in Example 1 produces.

[Table 7]

(COMPARATIVE EXAMPLE 3)

Apart from the fact that the core layer and the surface layer were formed as shown in Table 8 below, the composite was prepared in the same manner as in Example 1 provides.

When Polyether polyol, however, was polyether polyol with propylene oxide addition (available from Mitsui Chemicals, Inc., MN-300, hydroxyl number 560, Polyol equivalent 100).

[Table 8]

(COMPARATIVE EXAMPLE 4)

apart that the Core layer and the surface layer as shown formed in Table 9 below became the composite in the same manner as in Example 1 produces.

When Polyether polyol, however, was polyether polyol with added propylene (available from Sumitomo Bayer Urethane Ltd., SUMIPHEN 3900, hydroxyl number 35, polyol equivalent 1600).

[Table 9]

It were investigations of flexural strength, the proportional limit in compression, nail behavior and nail-pulling behavior that in Examples 1-5 and Comparative Examples 1-4 produced composites. The results are shown in Table 10. It was also an investigation of flexibility in Examples 14 and Comparative Examples 3 and 4, and Further, in Examples 1-3 and Comparative Example 1 examines the behavior of repeated nail pulling. These findings are also shown in Table 10.

The Flexural strength and the proportional limit in compression were according to the JIS Z 2101 prescribed method.

in the Regarding the nail behavior were prepared holes of Drilled 17 mm in diameter and 110 mm in depth, and then were through JIS E 1109 prescribed rail screw nails screwed into the prepared holes. The composites, which were not broken by the drilling, with a torque of at most 80 kN · m were tightened and in their surfaces by tightening the Screws no cracking were represented by 0, and all other composites as these were represented by ×.

dargestellt, nicht weniger als 33 kN wird durch

dargestellt, nicht weniger als 28 kN wird durch O dargestellt, nicht weniger als 23 kN wird durch Δ dargestellt, und weniger als 23 kN wird durch × dargestellt.With regard to the nail pulling behavior, the screw nails screwed in the nail behavior tests were pulled out. A load of not less than 38 kN is going through

shown, not less than 33 kN is going through

not less than 28 kN is represented by 0, not less than 23 kN is represented by Δ, and less than 23 kN is represented by ×.

dargestellt. Diejenigen, bei denen die Schraubnägel in mindestens 100000 bis höchstens 1000000 wiederholten Nagelziehvorgängen gezogen wurden, wurden durch O dargestellt, und diejenigen, bei denen die Schraubnägel in weniger als 100000 wiederholten Nagelziehvorgängen gezogen wurden, wurden durch × dargestellt.Repeated nail pulling behavior was evaluated by repeatedly pulling the threaded nails screwed in the nail pulling test tests with a maximum load of 20 kN and a sine wave of 3 Hz. Those composites in which no destruction was detected in one million repeated nail-pulling operations were performed

shown. Those in which the screw-nails were pulled in at least 100,000 to at most 1,000,000 repeated nail-pulling operations were represented by ○, and those in which the screw-nails were drawn in less than 100,000 repeated nail-pulling operations were represented by ×.

Flexibility:

It was calculated from the following equation, using the deflection at the center of the span = Δy, which corresponds to a permissible capacity at rated center of gravity when judging the flexural strength. Deflection (%) = 6 × (thickness of specimen) × Δy / (span) 2 × 100

[Table 10]

Out Table 10 it is found that the composites of the invention in terms of bending strength, pressure behavior, nail behavior and Nail pulling behavior were excellent.

(EXAMPLE 6)

After this the fillers dispersed in the thermosetting foam solution shown in Table 11 They were cast in the mold for 30 minutes Verschäumungs- and curing reaction at 100 ° C and thereby became a core layer of rectangular Cross section with a size of 200 × 100 mm generated.

Then were 110 parts by weight of the thermosetting given in Table 11 Urethane foam mixed solution over 110 Parts by weight of the long fibers shown in Table 11 sprayed to the Long fibers to be impregnated. Then, the long fibers became in the state of parallel alignment in the longitudinal direction of Core layer arranged so that they in a thickness of 20 mm (in the thickness direction) along the top and bottom lower surfaces The core layer extended and also in a thickness of 5 mm (in the width direction) along both side surfaces of the core layer. Then they were poured into the mold and foamed for 30 minutes at 80 ° C and hardened, and thereby became the composite having a cross-sectional size of 210 × 140 mm generated.

When Polyether polyol with propylene oxide additive in the thermosetting foam liquid the core layer was SUMIPHEN 1703, that of Sumitomo Bayer Urethane Ltd. (hydroxyl number 380, polyol equivalent 147).

[Table 11]

(EXAMPLE 7)

apart that the Core layer and the surface layer as shown formed in Table 12 below became the composite prepared in the same manner as in Example 6.

When Polyether polyol with propylene oxide additive in the thermosetting foam liquid The core layer was a mixture of 50 wt .-% SUMIPHEN 1703, available Sumitomo Bayer Urethane Ltd. (Hydroxyl number 380, polyol equivalent 147), and 50 wt% SUMIPHEN 3900, available from Sumitomo Bayer Urethane Ltd. (Hydroxyl number 35, polyol equivalent 1600).

[Table 12]

(COMPARATIVE EXAMPLE 5)

apart that the Core layer and the surface layer are given in Table 13 below, The composite was prepared in the same manner as in Example 6.

When Polyether polyol with propylene oxide additive in the thermosetting foam liquid the core layer was SUMIPHEN 1703, that of Sumitomo Bayer Urethane Ltd. (hydroxyl number 380, polyol equivalent 147).

[Table 13]

(COMPARATIVE EXAMPLE 6)

It was a molding material made exclusively by longitudinal fibers increased Foam with the same mixture preparation as that the surface layer of Example 6.

The proportionality in compression and nail behavior in Examples 6, 7 and Comparative Examples 5, 6 produced composites or molding materials were measured. In addition, the flexural strength, the flexural modulus and sag (%) at the singular point that produced in Examples 6, 7 and Comparative Example 5 Composites and the flexural modulus of the same composites increased Bend from the singular Point measured off. The results are shown in Table 14.

To note that the Flexural modulus at elevated Deflection from the slope of the tangent to the singular point calculated from the direction of the large deflection has been.

Flexural strength, Flexural modulus and proportionality limit when compressed, according to the method described by JIS Z 2101 prescribed method.

The deflection was from the equation Deflection (%) = 6 × (thickness of specimen) × Δy / (span) 2 × 100 calculated using the deflection at a mid-point of the span = Δy, which corresponds to an allowable capacity in the rated load center of gravity when judging the flexural strength.

The Core layer and the composite were in the longitudinal direction of the test piece bent in the vertical direction. With regard to the composite was the orientation direction of the long fibers contained in the surface layer as a longitudinal direction of the test piece taken.

dargestellt und weniger als 23 kN ist durch × dargestellt.Regarding the nail pulling performance, after drilling the prepared holes having a diameter of 17 mm and a depth of 110 mm in the surface layer of the specimen covered with the surface layer, the rail screw nails prescribed by JIS E 1109 were hammered 20 mm up to their head grooves. Then, the nail pulling resistance values were measured at a speed of 10 mm / min. A load of not less than 23 kN is represented by Δ, not less than 28 kN is represented by O, not less than 33 kN is by

and less than 23 kN is represented by ×.

[Table 14]

you will recognize from Table 14 that the thus-constructed composite of the invention excellent bending strength and pressure resistance, improved printing properties, especially in comparison with the material with only one surface layer and without a core layer, and produce excellent nail pulling properties and therefore can be effectively used as synthetic wood, especially for rail sleepers.

(EXAMPLE 8)

A filler heat-curable foam layer of the same type as that used to form the core layer of Example 6 first as first filler-containing Layered material poured into the mold and then leveled. After that became a filler-containing thermosetting foam liquid of the same kind as the second filler-containing sheet material poured in the mold. Then the materials were allowed to stand for 30 minutes 100 ° C one Verschäumungs- and curing reaction and thereby the core layer was produced the first filler-containing Layer of rectangular cross section with a size of 200 × 100 mm and a thickness of 50 mm and the second filler-containing layer with a thickness of 50 mm, the layers being laminated.

Then became the composite with the surface layer, which coincides with a Thickness of 20 mm along the top and bottom surfaces of the Core layer and with a thickness of 5 mm along both side surfaces of the Core layer extends and identical in construction with that of Example 6 is and has a cross-sectional size of 210 x 140 mm, to which same way as in Example 6 poured.

(EXAMPLE 9)

A filler thermosetting Foam layer of the same kind as those used for molding The core layer of Example 6 was initially used as first filler Layered material in the mold and was then at 30 minutes 100 ° C the Verschäumungs- and curing reaction to thereby produce a laminated material having a first filler-containing Layer of rectangular cross section with a size of 200 × 50 mm is.

Subsequently was a first intermediate material with a size of 210 × 75 mm, the one with long fibers increased Layer had, with a thickness of 20 mm along a upper surface of the layer material, with a thickness of 5 mm along a bottom area of the material and with a thickness of 5 mm along both side surfaces of the Stretched material under the same conditions as for the surface layer according to example 6 produced.

Then, a filler-containing thermosetting foam liquid of the same kind as that used to form the core layer of Example 2 was first added as the second filler-containing Layered material is poured into the mold and then subjected to a foaming and curing reaction at 100 ° C for 30 minutes to thereby produce a layered material which is a second filler-containing layer of rectangular cross section having a size of 200 x 50 mm.

Subsequently was a second intermediate material with a size of 210 × 65 mm, the one with long fibers increased Layer had a thickness of 5 mm along a upper surface of the layer material, with a thickness of 5 mm along a bottom Flat of the layer material and with a thickness of 5 mm along both side surfaces of the layered material under the same conditions like those for the surface layer produced by Example 6.

Then was epoxy adhesive (ESURON 410, available from Sekisui Chemical Co., Ltd.) on an underside of the first manufactured in this way Intermediate material and a top of the made in this way applied second intermediate material. These surfaces were brought into pressure contact with each other at room temperature for 24 hours, to thereby produce a composite comprising a fiber-reinforced interlayer with a thickness of 10 mm between the first filler-containing layer and the second filler-containing Layer had.

Flexural strength, Flexural modulus, nail pull and deflection in the examples 8 and 9 composites were investigated. The results are shown in Table 15, along with those of the composite of example 6.

dargestellt, nicht weniger als 38 kN wird durch

dargestellt, nicht weniger als 43 kN wird durch

dargestellt, und weniger als 23 kN wird durch × dargestellt.With regard to the nail pulling performance, after drilling the prepared holes having a diameter of 17 mm and a depth of 120 mm in the surface of the surface-covered specimen, the rail screw nails prescribed by JIS E 1109 were beaten 20 mm up to their head grooves. Then nail pulling resistance values were measured at a speed of 10 mm / min. A load of not less than 23 kN is represented by Δ, not less than 28 kN is represented by O, not less than 33 kN is transmitted

represented, not less than 38 kN is going through

represented, no less than 43 kN is going through

and less than 23 kN is represented by ×.

[Table 15]

you will recognize from Table 15 that the composite with the Core layer formed by laminating several core layer forming Compound layers is formed, compared to the composite with the core layer of a single-layered structure improved Bending strength offers. Furthermore, the core layer, which with the fiber reinforced Intermediate layer between the filler-containing Layer and the filler Layer is formed, also an improved nail pulling behavior.

(EXAMPLE 10)

As shown in Table 16, was raw material of vinyl chloride foam, in which 0.05 parts by weight of ADCA (azodicarbonamide) as a foaming agent 100 parts by weight of vinyl chloride resin (PVC composition, available from Tokuyama Sekisui Co., Ltd.), in the form of a chalkboard-like Extruded molding with a cross-sectional size of 160 × 100 mm, the Core layer forms.

The panel-like molding was molded using the in 3 The long fiber production unit 4 and the thermosetting foam liquid shown in Table 16 are surrounded to produce a composite having a cross-sectional size of 200 × 140 mm having a surface layer around the core layer having the cross-sectional size of 160 × 100 mm.

[Table 16]

(EXAMPLE 11)

A composite having a cross-sectional size of 200 × 140 mm having a long fiber surface layer and the thermosetting foam liquid shown in Table 17 to surround the core layer having a cross-sectional size of 160 mm × 100 mm containing the thermosetting foam liquid and the following Table 17 has been specified with the in 3 produced production unit 4 produced. The molded article extruded from the die mouthpiece had a cross section of 160 × 100 mm.

[Table 17]

(EXAMPLE 12)

A composite having a cross-sectional size of 200 × 140 mm having the surface layer with the long fibers and the thermosetting foam liquid shown in Table 18 to surround the core layer having a cross-sectional size of 160 × 100 mm containing the thermosetting foam liquid and the following Table 18) was filled with the in 3 produced production unit 4 produced. The molded article extruded from the die mouthpiece had a cross section of 160 × 100 mm.

[Table 18]

(COMPARATIVE EXAMPLE 7)

It a composite with a cross-sectional size of 200 × 140 mm was made only the long fibers and thermosetting foam liquid exhibited for the surface layer of Example 10 were used.

(COMPARATIVE EXAMPLE 8)

As shown in Table 19, after preheating a mixture of 20 parts by weight of resole-based phenol particles (BERU PAARU (article name), available from KANEBO, Ltd.) and 80 parts by weight of quartz sand No. 5, the mixture was set at 200 ° C at 20 kg / cm ² , thereby producing a porous material which is the core layer having a cross-sectional size of 160 × 100 mm.

This porous material was prepared using the in 3 4 and the long fiber and thermosetting foam liquid shown in Table 19 are formed to prepare a composite having a cross-sectional size of 200 × 140 mm having a surface layer around the core layer having the cross-sectional size of 160 × 100 mm.

[Table 19]

(COMPARATIVE EXAMPLE 9)

As shown in Table 20, polystyrene resin (available from Sumitomo Chemical Co., Ltd.) extruded and foamed to a low-power To produce polystyrene foam, the core layer with a Cross-sectional size of 160 × 100 mm forms.

This foam was made using the in 3 and the heat-curable foam liquid shown in Table 20 was formed to produce a composite having a cross-sectional size of 200 × 140 mm having a surface layer around the core layer having the cross-sectional size of 160 × 100 mm.

[Table 20]

(COMPARATIVE EXAMPLE 10)

elastic Urethane foam, which forms the core layer of 160 × 100 mm, was under Use of urethane resin having the composition shown in Table 21 produced.

This elastic urethane foam was prepared using the in 3 and the heat-curable foam liquid shown in Table 21 to produce a composite having a cross-sectional size of 200 × 140 mm having a surface layer around the core layer having the cross-sectional size of 160 × 100 mm.

[Table 21]

The Ca, Cb, CSa, CSb, Ea, Eb, ESa, ESb, DBa values, flexural strength, nail performance, and nail-pulling performance of those in Examples 10-12 and Comparative Examples 7-10 manufactured Ver Composites were investigated. The results are shown in Table 22.

[Table 22]

Out Table 22 clearly shows that the adjustment of CSa, CSb, Ea, Eb, ESa, ESb and DBa on the structure of the composite according to claims 10 and 11, a volume reduction of the surface layer allows and an improvement in flexural strength, flexibility and flexibility the proportionality limit in compression, nail behavior and nail-pulling behavior achieved.

(EXAMPLE 13)

A composite having a cross-sectional size of 200 × 140 mm and a length of 2020 mm, which is a core layer having a cross-sectional size of 180 × 100 mm shown in Table 23 below, an intermediate layer comprising a non-foamed urethane resin having a thickness of about 2 mm and polyester fiber nonwoven fabric (SUPAN BONDO E 1050, available from Asahi Chemical Industrial Co., Ltd.) as a resin-impregnated film-like material and had a surface layer shown in Table 23, was coated with the in 3 produced vertical production line shown.

[Table 23]

By microscopic examination of the resulting composite at or near the interface between the core layer and the surface layer was the presence the intermediate layer in which the resin impregnated film-like Material was arranged.

(EXAMPLE 14)

apart that the surface layer given in Table 24 below, Interlayer and core layer were formed, became a composite prepared in the same manner as in Example 13.

It it was found that between the core layer and the surface layer an intermediate layer of about 3 mm thickness of epoxy resin was formed.

[Table 24]

(REFERENCE EXAMPLE 1)

Apart from the fact that no intermediate layer was provided, a composite material was used 1i with a core layer 2i and a surface layer 3i , as in 14 shown in the same manner as in Example 13.

(REFERENCE EXAMPLE 2)

As in 15 shown, became a composite 1j produced solely from the surface layer of Example 13.

It were the shear strength of the interface between the core layer and the surface layer of each of the composites measured from Examples 13, 14 and Reference Examples 1, 2 were obtained. The results are shown in Table 25, along with the results for flexural strength, the flexural modulus, the compressive strength (JIS K 2101) and the wood workability, such as cutting.

The Shear strength was as prescribed by JIS Z 2101 Method with a TENSIRON UCT-5T device manufactured by Orientec Co., Ltd., measured at a crosshead speed of 1 mm / min.

[Table 25]

It is clearly apparent from Table 25 that the composite having the interlayer provided between the surface layer and the core layer and through which the core layer and the surface layer are formed The composite layer of claim 13, can provide a much higher interfacial strength than the composite having no surface layer, and further, as one of various applications, can be fully applicable to the SEW process.

(EXAMPLE 15)

apart that the surface layer given in Table 26 below, Interlayer and core layer were formed, became a composite prepared in the same manner as in Example 13.

When Polyether polyol with addition of propylene oxide was SUMIPHEN 1703 (hydroxyl number 380, polyol equivalent 147), available from Sumitomo Bayer Urethane Ltd., used.

It it was found that the Composite produced a core layer with a shear strength of 6 MPa, a surface layer with a shear strength of 8 MPa and an intervening Intermediate layer with a thickness of 1 mm, the low-power Foam with a density of 0.50 existed by the factor 1.1 higher was as in the core layer.

[Table 26]

(EXAMPLE 16)

apart that surface layer, Intermediate layer and core layer were formed as in the following Table 27 stated that a composite was made in the same way as prepared in Example 13.

It it was found that the produced plastic a core layer with a shear strength of 6 MPa, a surface layer with a shear strength of 8 MPa and interlayer sections with a thickness of 1 mm, between the core layer and the nonwoven fabric or between the nonwoven fabric and the surface layer were trained and had a density of 0.50 by the factor 1.1 higher as was in the core layer.

[Table 27]

(EXAMPLE 17)

apart that surface layer, Intermediate layer and core layer were formed, as in the following Table 28, a composite was made in the same way as prepared in Example 13.

It it was found that the Composite a core layer with a shear strength of 6 MPa, a surface layer with a shear strength of 8 MPa and interlayer sections with a thickness of 1 mm, between the core layer and the nonwoven fabric or between the nonwoven fabric and the surface layer were trained and had a density of 0.48, by the factor 1.1 higher as was in the core layer.

[Table 28]

The composites obtained in Examples 15-17 and Comparative Example 5 were subjected to shear tests according to the method prescribed in JIS Z 2101, after which a compressive force was applied to the composite in the direction parallel to the fiber extension direction in such a manner as in an intermediate layer portion 7k between a core layer 2k and a surface layer 3k a fracture surface could arise, as in 16 shown. The measurement results are shown in Table 29. In addition, the flexural strength and the flexural modulus were measured according to the method prescribed by JIS Z 2101; the results are given in Table 29 together with the results of the flexural fatigue tests.

dargestellt, weniger als 1 × 10⁷ bis nicht weniger als 1 × 10⁶ wird durch O dargestellt, und weniger als 1 × 10⁶ wird durch × dargestellt. Ferner wird hinsichtlich der Zerstörung der Fall der durch die Oberflächenschicht verursachten Zerstörung durch × dargestellt, und der Fall, wo zwischen der Oberflächenschicht und der Kernschicht keine Zerstörung festgestellt wird, oder der Fall, wo durch wiederholtes Biegen mit einer Biegewechselzahl von nicht weniger als 1 × 10⁷ keine Zerstörung verursacht wird, wird durch O dargestellt.It should be noted that the fatigue bending tests according to the flexural fatigue tests were carried out with constant tension at a span of 1960 mm, a bending stress of 60 MPa and a frequency of 6 Hz. A number of bending cycles of not less than 1 × 10 to break is achieved

less than 1 × 10 ⁷ to not less than 1 × 10 ⁶ is represented by O, and less than 1 × 10 ⁶ is represented by ×. Further, with respect to the destruction, the case of destruction caused by the surface layer is represented by ×, and the case where no destruction is found between the surface layer and the core layer, or the case where repeated bending with a number of bending cycles of not less than 1 × 10 ⁷ no destruction is caused, is represented by O.

[Table 29]

Out Table 29 clearly shows that the composite according to claim 20 excellent properties not only in terms of bending strength and the bending modulus, but also in terms of durability at repeated Bending offers.

USE POSSIBILITIES IN INDUSTRY

Of the thus constructed composite according to the invention can further improve pressure resistance and nail behavior achieve.

If the composite used as rail sleepers and the like it can easily dampen vibrations to reduce noise to reach. There as well the core layer in case of damage Wear resistant to destruction is, the damage will be then on the surface layer caused and is therefore easily recognizable.

Further The relative density of the composite produced can be light by adjusting the specific gravity of fillers of the core layer so that the Composite for Different uses can be made of the mass-saving Application to the mass-loaded application range.

at the structure according to claim In particular, 5 comes the thermal expansion coefficient the core layer that of the surface layer Near. As a result, even when the ambient temperature arises varies greatly, with little deformation at an interface between the surface layer and the core layer, and in this way, a high reliability the long-term adhesive properties provided between the layers.

at the structure according to claim 6 becomes the resistance improved against repeated nail pulling, which leads to the result that in use of the composite as rail sleepers, the maintenance interval for the rail sleepers extended can be.

at the structure according to claim 9 becomes a destruction the core layer is suppressed, which gives the flexibility as well as the bending strength, the proportional limit of compression, the Improve nail behavior and nail-pulling behavior. Using the composite as rail sleepers and the like can the Composite therefore for noise reduction Slightly dampen vibrations. There as well the core layer in case of damage resistant to wear due to wear destruction is, the damage will be then on the surface layer caused and is therefore easily recognizable.

at The structure according to claims 14 and, the composite may suitably be for a railroad tie (especially a railway sleeper), a pressure-absorbing plate and a shield lift (SEW) extraction / access sealing wall is used which have a high flexural strength and a high flexural modulus require. There as well for purposes which do not require high bending strength and high flexural modulus, reduces the product size can be, can be achieve a material cost savings. Because the fiber reinforced interlayer between the filler-containing Layer and the filler-containing layer is provided, as well a hammered nail through the long fibers of the fiber-reinforced intermediate layer be bound to provide an improved nail-holding ability.

at the structure according to claim 18 will be the destruction the core layer is suppressed, whereby an improvement of the flexibility and the flexural strength, the proportionality limit in compression, nail behavior and nail pulling behavior be achieved. Therefore, the composite can be used as rail sleepers and the like for noise reduction Dampen vibrations even more easily.

In the structure according to claim 19, the core layer and the surface layer are integrated by the unfoamed thermosetting resin layer, thereby providing excellent interfacial strength is provided.

at Use as material for the SEW design, which is one of several applications of the composite The composite may be used alone as a unit be without several flat sheets are laminated and glued together under pressure have to, unlike the conventional one Art wood. Therefore, the bonding operation can be omitted, and it may be the same or higher Strength can be achieved than that of conventional synthetic wood.

at the structure according to claim 20 may in particular the durability against continuous bending stress be improved so that the Composite is even better than building material, such. B. as wall material for the SEW design and as a railway sleeper, which has a high durability against continuous bending stress require.

at the structure according to claim 21 can by a high-strength film and the like, which are resin impregnated Foil is used, a higher Strength of the intermediate layer are made possible.

at the formation of the intermediate layer, the resinous foil-like Material with an unfoamed thermosetting Resin impregnated to facilitate the formation of the intermediate layer.

at the structure according to claim 22 can be a composite of higher mechanical strength are produced, which is easy to foam Closed cells can form and an excellent low absorption capacity having.

at the structure according to claim 26, even more stable flexural strength can be produced.

The synthetic rail sleeper according to claim 27, for which the above-mentioned composite according to the invention is used, has the same outstanding capabilities as natural wood. It has excellent interfacial adhesion, in other words excellent interfacial strength.

1a, 1b, 1c, 1d, 1e, 1f, 1h, 1i and 1j

composite

2a, 2b, 2c, 2d, 2e, 2f, 2g, 2h, 2i and 2k

core layer

22

filler

23 24 and 26

filler Layer (core layer-forming composition)

25

fiber reinforced intermediate layer (core layer forming composition)

3a, 3b, 3c, 3g, 3h, 3i and 3k

surface layer

5, 81

long fiber

7h, 7k

interlayer

P

singular point

T

tangent (Tangent to the singular Point P)

87

resin-impregnated sheet-like material

Claims (21)

Composite comprising: a core layer ( 2 ); and a surface layer ( 3 ) comprising a thermosetting resin, which is supported by long fibers ( 5 ), which is strengthened parallel in their longitudinal direction, the surface layer ( 3 ) on the core layer ( 2 ) is laminated to at least one surface of the core layer ( 2 ), characterized in that the core layer ( 2 ) a synthetic resin ( 21 ), the filler ( 22 containing by weight greater than or equal to 0.7 times the product of the volume of the core layer ( 2 ) and the bulk density of the filler ( 22 ). Composite according to claim 1, characterized in that the thermosetting resin of the surface layer ( 3 ) contains light filler. Composite according to claim 1 or 2, characterized in that the surface layer ( 3 ) has a density of 0.3 g / cm ³ to 1.5 g / cm ³ . Composite according to one of Claims 1 to 3, characterized in that the surface layer ( 3 ) has a flexural modulus of at least 6000 MPa and a flexural strength of at least 100 MPa. Composite according to one of Claims 1 to 4, characterized in that the filler ( 22 ) has an average particle size of at least 0.5 mm. Composite according to one of Claims 1 to 5, characterized in that the filler ( 22 ) at a particle size distribution curve in which the particle size on the abscissa and a volume ratio of the filler per particle size to all fillers are plotted on the ordinate, has two or more peak areas making up at least 8% by volume, and also has a size distribution the most common particle size values in the smaller peak area of at least 8% by volume are at most 0.7 times the most common particle size values in the larger peak area of at least 8% by volume closest to the smaller peak area. Composite according to one of Claims 1 to 6, characterized in that the synthetic resin ( 21 ), which is the core layer ( 2 ) is thermosetting resin. Composite according to one of Claims 1 to 6, characterized in that the synthetic resin ( 21 ), which is the core layer ( 2 ), is thermoplastic resin. Composite material according to one of Claims 1 to 7, characterized in that the synthetic resin ( 21 ), which is the core layer ( 2 ), thermoplastic polyurethane resin foam having a polyol equivalent of at least 230 to at most 1500, or thermosetting polyurethane foam having a density of at least 0.3 g / cm ³ and a polyol equivalent of at most 1500. Composite according to one of Claims 1 to 9, characterized in that the core layer ( 2 ) through several core layers ( 23 . 24 ) forming a composite layer ( 23 . 24 ) form. Composite according to Claim 10, characterized in that one of the layers ( 23 . 24 thermosetting resin composite layers reinforced by long fibers running parallel in their longitudinal direction or made of lightweight filler-containing thermosetting resin reinforced by long fibers running parallel in their longitudinal direction. Composite according to one of Claims 1 to 11, characterized in that the core layer ( 2 ) has a compressive shear strength DPa of at least 5 MPa. Composite according to one of Claims 1 to 12, characterized in that the core layer ( 2 ) and the surface layer ( 3 ) by an intermediate layer ( 7 ) having foam-free thermosetting resin or low-power resin foam are bonded together in one piece. Composite according to claim 13, characterized in that an intermediate layer section ( 7 ) has a compressive shear strength of at least 6 MPa, or that the surface layer ( 3 ) and the core layer ( 2 ) both have a compressive shear strength of at least 6 MPa when attached to the composite ( 1 ) in a direction to the fiber direction of the long fibers ( 5 ) of the surface layer ( 3 ) parallel direction acts a compressive force, so that a fracture surface in the intermediate layer section ( 7 ) and the composite ( 1 ) has the physical property that either the surface layer ( 3 ) or the core layer ( 2 ) first breaks when the compressive force on the composite ( 1 ) in the fiber direction of the long fibers ( 5 ) of the surface layer ( 3 ) parallel direction, so that the fracture surface in the interlayer section ( 7 ) can arise. Composite according to Claim 13 or 14, characterized in that a resin-impregnated plate-like material is present in the intermediate layer ( 7 ) is arranged. Composite according to any one of the preceding claims with the exception of claim 8 and any claim dependent on claim 8, characterized in that the synthetic resin ( 21 ) of the core layer ( 2 Polyurethane resin foam and surface layer resin ( 3 ) Is polyurethane resin sheeting. Composite according to one of Claims 1 to 16, characterized in that the material has a total thickness of at least 100 mm and a ratio between a thickness of the core layer ( 2 ) and a total thickness of the surface layer ( 3 ), which the core layer ( 2 ) is covered in the thickness direction, in the range of 9/1 to 1/1. Composite according to claim 11 or 17, characterized in that the core layer ( 2 ) at least two layers ( 23 . 24 ) from core layer-forming compositions comprising filler and synthetic resin, and at least one layer ( 25 ) of thermosetting resin core layer-forming composition reinforced by long fibers interposed between the two core layer-forming compositions ( 23 . 24 ) of at least two layers of core layer-forming compositions are inserted and parallel in a longitudinal direction of the composite ( 1 ), and wherein a ratio between a total thickness of the core layer ( 2 ) forming composition layer ( 23 . 24 ) and a total thickness of the core layer ( 2 ) forming composition layer ( 25 ) ranges from 95/5 to 50/50. Composite according to one of Claims 1 to 18, characterized in that the surface layer ( 3 ) on the core layer ( 2 ) is laminated to at least two surfaces of the core layer ( 2 ) to cover; that the composite ( 1 ) has a total thickness of at least 100 mm, and that a thickness of the surface layer ( 3 ) on a side to which a tensile force is applied when the composite ( 1 ) is bent in the thickness direction, is at least 5% to at most 25% of the total thickness and the thickness of the surface layer ( 3 ) is at least 1.5% to at most 15% of the total thickness on the side to which a compressive force is applied. Composite according to one of Claims 1 to 19, characterized in that the surface layer ( 3 ) four surfaces of the core layer ( 2 ) and at least 10% by volume to at most 65% by volume of the total composite ( 1 ). Synthetic threshold, which is a composite after one of the claims 1 to 20.