Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/38—Fibrous materials; Whiskers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B16/04—Macromolecular compounds
  • C04B16/06—Macromolecular compounds fibrous
  • C04B16/0675—Macromolecular compounds fibrous from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B18/02—Agglomerated materials, e.g. artificial aggregates
  • C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/0048—Fibrous materials
  • C04B20/0068—Composite fibres, e.g. fibres with a core and sheath of different material
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/10—Coating or impregnating
  • C04B20/1018—Coating or impregnating with organic materials
  • C04B20/1029—Macromolecular compounds
  • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/395—Isocyanates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/55—Epoxy resins

Definitions

• the present invention relates to a fiber material suitable for cement reinforcement. It more specifically relates to a fiber material for cement reinforcement, which is optimal for the production of concrete, mortar, and the like.
• Concrete or mortar formed products containing cement as a main component have compressive strength, durability, non-flammability, and like excellent characteristics and are also inexpensive, and thus have been abundantly used in the architectural and civil engineering fields.
• these formed products have drawbacks in that their physical properties are basically brittle even when aggregates such as sand and gravel are contained, and they are easily cracked or damaged, for example, upon application of a stress, such as pulling, bending, or flection.
• fibrous materials such as asbestos, glass fibers, steel fibers, and synthetic fibers as reinforcing materials in addition to various conventional aggregates, thereby improving the performance of a formed product.
• fibrous reinforcing material By using a fibrous reinforcing material, the mechanical characteristics, such as bending strength and bending toughness, of a cement formed body made of cement paste, mortar, concrete, or the like are significantly improved.
• PTL 1 discloses a method in which non-volatile oil is attached to fibers bundled with a resin, thereby enhancing the cohesion of fibers.
• the attachment of oil to the fiber surface although the cohesion is excellent, the interfacial attachment strength between cement mortar or concrete and fibers tends to rather decrease.
• PTL 2 discloses a reinforcing material obtained by bundling fibers with a carboxyl-group-containing acrylic-modified resin, thereby maintaining relatively excellent cohesion in cement mortar.
• a carboxyl-group-containing acrylic-modified resin has high affinity for cement, it has been difficult to enhance the cohesive strength of the resin layer present on the adhesion interface.
• An object of the invention is to provide a fiber material for cement reinforcement having high cohesion and an excellent reinforcing effect, and particularly to provide a fiber material for cement reinforcement having an excellent reinforcing effect on high-viscosity concrete or mortar.
• the fiber material for cement reinforcement of the invention is characterized in that a resin A containing an isocyanate compound as a constituent component is present inside a fiber bundled body, and a resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body.
• the resin A contains a polyol or an epoxy compound as a constituent component in addition to the isocyanate compound
• the resin B contains an acrylic-modified epoxy resin or a bisphenol-A epoxy resin as a main component
• the isocyanate compound in the resin A is a blocked isocyanate compound.
• the fiber bundled body has a tensile strength of 7 cN/dtex or more, and the fiber bundled body includes 50 to 3,000 single fibers.
• the invention also encompasses a concrete or mortar formed body containing the fiber material for cement reinforcement of the invention described above, which preferably further contains aggregates. Then, it is preferable that a method for producing such a concrete or mortar formed body is a production method in which the fiber material for cement reinforcement of the invention described above is contained, and the water/binder ratio at the time of kneading is 45% or less.
• a fiber material for cement reinforcement having high cohesion and an excellent reinforcing effect particularly a fiber material for cement reinforcement having an excellent reinforcing effect on high-viscosity concrete or mortar, is provided.
• the fiber material for cement reinforcement of the invention is a reinforcing material configured such that a resin A containing an isocyanate compound as a constituent component is present inside a fiber bundled body, and a resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body.
• the fiber bundled body used for such a fiber material for cement reinforcement of the invention is not particularly limited as long as it is a fibrous material (multifilament) formed of a large number of single fibers (monofilaments) bundled, and various inorganic fibers and organic fibers (organic synthetic fiber) are usable.
• fibers used for the fiber bundled body include inorganic fibers, such as carbon fibers, glass fibers, basalt fibers, steel fibers, ceramic fibers, and asbestos fibers, and organic fibers, such as aromatic polyamide fibers (hereinafter referred to as aramid fibers), vinylon fibers, polypropylene fibers, polyethylene fibers, polyarylate fibers, polybenzoxazole (PBO) fibers, nylon fibers, polyester fibers, acrylic fibers, vinyl chloride fibers, polyketone fibers, cellulose fibers, and pulp fibers. These fibers maybe used alone or in combination of two or more kinds.
• inorganic fibers such as carbon fibers, glass fibers, basalt fibers, steel fibers, ceramic fibers, and asbestos fibers
• organic fibers such as aromatic polyamide fibers (hereinafter referred to as aramid fibers), vinylon fibers, polypropylene fibers, polyethylene fibers, polyarylate fibers, polybenzoxazole (PBO) fibers, nylon fibers
• the fiber used for the fiber material for cement reinforcement of the invention is a fiber that undergoes less degradation in an alkali.
• inorganic fibers carbon fibers, basalt fibers, and the like are preferable.
• organic fibers aramid fibers (aromatic polyamide fibers), vinylon fibers, polyethylene fibers, polypropylene fibers, and the like are preferable.
• carbon fibers or aramid fibers having a high reinforcing effect in terms of bending toughness, etc. are used to form a fiber bundle.
• the fiber used in the invention is an organic fiber using a resin produced using an organic polymer as a starting material.
• the fiber has excellent flexibility and is resistant to bending during the process, and thus is useful.
• aramid fibers, vinylon fibers, polyethylene fibers, polypropylene fibers, and the like, which are high-strength organic fibers are preferable. This is because such an organic fiber undergoes less breakage during kneading or less strength deterioration due to corrosion or the like in concrete, eventually exhibiting an excellent reinforcing effect on a cement material.
• a polyethylene fiber it is preferable use ultra high-molecular-weight polyethylene.
• para-type aramid fibers such as polyparaphenylene terephthalamide are preferable.
• copolymerized aramid fibers have particularly excellent alkali resistance and thus are particularly preferably used.
• a copolyparaphenylene-3,4′-oxydiphenylene-terephthalamide fiber which is a copolymerized para-type aramid fiber, has a high reinforcing effect in cement as compared with other fibers and thus is preferable.
• the fiber when the fiber is allowed to stand in a strong-alkali atmosphere at high temperatures and high pressures for a long period of time, its mechanical characteristics are not significantly degraded.
• the strength retention of the fiber in steam curing at high temperatures and high pressures for example, under conditions of 120° C., saturation water vapor, and 100 hours, is as high as 70% or more. Further, it is preferable that the fiber has a strength retention of 90 to 100%.
• the single-yarn fineness of each fiber forming the fiber bundled body is 0.5 to 100 dtex.
• the single-yarn fineness is too low, it is difficult to align single yarns. Then, when the alignment of single yarns is insufficient, it tends to happen that the mechanical performance of the fiber cannot be sufficiently utilized.
• the single-yarn fineness is low, the attachment of a bundling agent tends to be non-uniform, and predetermined cohesion may not be obtained.
• the number of single yarns is too large, the cohesion tends to decrease. Meanwhile, in the case where the single-yarn fineness is too large, the adhesion area between single yarns is reduced.
• the single-yarn fineness of each single yarn forming the bundled body is 0.6 to 80 dtex.
• the upper limit is 50 dtex or less, particularly preferably 6.0 dtex or less.
• the lower limit is 1.5 dtex or more, particularly preferably 1.5 to 3.0 dtex.
• the fiber bundled body used in the invention is a collection of single yarns as described above, and preferably includes 50 to 3,000 single fibers. It is still more preferable that the fiber bundled body includes 100 to 1,500 single fibers. It is more preferable that the number of single fibers is 250 to 1100, particularly preferably within a range of 500 to 1,100.
• such a multifilament-type fiber bundle is used.
• a monofilament-type fiber having a large fiber diameter is used as a fiber bundled body.
• a monofilament-type fiber which is once wound up as a single monofilament after spinning, with an increase in the fiber diameter, it becomes more difficult to produce a high-strength fiber.
• the fiber bundled body used in the invention is non-twisted or has a twist coefficient of less than 3 (within a range of 0 to 3). Such twisting further improves the reinforcing effect.
• the twist coefficient is too large, the strength tends to decrease. This is because as a result of twisting, at the time of pulling, a higher force perpendicular to the direction of the fiber axis is caused by single yarns. This phenomenon is particularly prominent in fibers having poor flexibility.
• the twist coefficient is too large, the impregnation with a bundling agent tends to be non-uniform, and the elongation tends to increase due to twist shrinkage.
• the twist coefficient is preferably less than 2 (within a range of 0 to 2). Further, it is preferable that the twist coefficient is within a range of 1.0 to 2.0, and it is particularly preferable that the twist coefficient is 1.5 to 2.0.
• the twist coefficient is preferably less than 2 (within a range of 0 to 2).
• the twist coefficient is within a range of 1.0 to 2.0, and it is particularly preferable that the twist coefficient is 1.5 to 2.0.
• the fiber used in the invention has high strength. More specifically, it is preferable that the fiber has a tensile strength of 7 cN/dtex or more. It is still more preferable that the tensile strength is within a range of 10 to 40 cN/dtex, particularly 20 to 40 cN/dtex.
• the tensile strength of the fiber is too low, when a load is applied to cement mortar or concrete, the bending strength of the formed product tends to be low, or, due to fiber breakage, it tends to happen that the impact cannot be sufficiently absorbed.
• the fiber material for cement reinforcement of the invention is configured such that a resin A containing an isocyanate compound as a constituent component is present inside the fiber bundled body described above, and a resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body. Further, it is preferable that the resin A contains a polyol or an epoxy compound as a constituent component in addition to the isocyanate compound.
• the resin A present inside the fiber bundled body serves as a bundling agent for fibers.
• the resin A is a component containing an isocyanate compound as a constituent component.
• the resin A penetrates inside the fiber bundle and also adheres single yarns together in the fiber bundle, thereby facilitating firm bundling.
• the resin A is a resin having high toughness. More specifically, it is preferable that the resin A is an isocyanate resin, a polyurethane resin, a urea resin, a crosslinked isocyanate-epoxy, or the like.
• an isocyanate resin, a urea resin, and a crosslinked isocyanate-epoxy are preferable.
• the method for bundling fibers with the resin A is not particularly limited, and a method in which a fiber bundle is immersed in a solution of the resin A dissolved in an organic solvent such as toluene, followed by a heat treatment, thereby giving a fiber bundled body utilizing the self-crosslinking of the resin A, etc., a method in which a fiber bundle is immersed in an aqueous dispersion of the resin A, followed by a heat treatment, thereby giving a fiber bundled body utilizing the self-crosslinking of the resin A, etc., and the like can be mentioned.
• a water-based agent it is preferable to use a water-based agent.
• an isocyanate resin is used as the resin A
• a method in which a fiber bundle is immersed in a solution of an isocyanate compound dissolved in an organic solvent such as toluene, followed by a heat treatment, thereby giving a fiber bundled body utilizing the self-crosslinking of the isocyanate compound a method in which a fiber bundle is immersed in an aqueous dispersion of a waterborne blocked isocyanate, followed by a heat treatment, thereby giving a fiber bundled body utilizing the self-crosslinking of the isocyanate compound from which the blocking agent has been dissociated, and the like can be mentioned.
• the isocyanate compound in the resin A used in the invention is a blocked isocyanate compound.
• the isocyanate does not react with water until the step of evaporating moisture. Accordingly, the deactivation of functional groups in steps before that, such as the immersion step, can be suppressed.
• the isocyanate compound is selected from aromatic compounds, such as diphenylmethane diisocyanate and toluene diisocyanate, and aliphatic compounds, such as hexamethylene diisocyanate. Still more preferably, it is recommended to use an aliphatic isocyanate having excellent penetration into a fiber bundle. Further, it is preferable that such a compound has a dimer structure or a trimer structure. In addition, it is also preferable that the compound has a highly reactive, tri- or higher functional isocyanate group. Specifically, compounds having a hexamethylene diisocyanate (HDI) trimer structure, for example, are preferable.
• a trimer structure is a compound having, as its basic structure, acyclic structure formed of three NCO groups at the HDI terminal.
• the isocyanate compound is a blocked isocyanate compound
• compounds for blocking isocyanate groups specifically, dimethylpyrazole-blocked, methyl-ethyl-ketone-oxime blocked, caprolactam-blocked, and like blocked isocyanates are preferable.
• a dimethylpyrazole-blocked isocyanate compound particularly dimethylpyrazole-blocked hexamethylene diisocyanate.
• a dimethylpyrazole-blocked compound is a heterocyclic compound containing a nitrogen atom and the like in the cyclic structure in addition to a carbon atom, and is likely to have a resonance structure.
• the blocked compound is unblocked at lower temperatures, and thus such a compound is more preferably used.
• a compound blocked with dimethylpyrazole or the like and having an aliphatic tri- or higher functional isocyanate group it is preferable to use a compound blocked with dimethylpyrazole or the like and having an aliphatic tri- or higher functional isocyanate group (dimethylpyrazole block-HDI trimmer, etc.).
• Such a dimethylpyrazole-blocked isocyanate compound has high compatibility with the fiber-forming polymer. Then, when the fiber having attached thereto such a compound is heat-treated, and, according to the thermal history, the compound is allowed to thermally diffuse into the fibers over a sufficient period of time, resulting in high interface-reinforcing ability.
• a polyurethane resin is a resin obtained by the condensation of a polyol and an isocyanate compound. Then, as a method for using such a resin, it is possible to employ a method in which a fiber bundle is immersed in a solution of a polyol and an isocyanate dissolved in an organic solvent or a solution containing an aqueous dispersion of a waterborne polyol and a waterborne blocked isocyanate, followed by a heat treatment, thereby giving a fiber bundled body; a method in which fibers are immersed in a solution of a pre-condensed urethane resin dissolved in an organic solvent or in an aqueous dispersion thereof, and then the organic solvent or water is dried, thereby giving a fiber bundled body; or the like.
• a urea resin is a resin obtained by the condensation of a polyol and an isocyanate compound. Then, as a method for using such a resin, it is possible to employ a method in which
• the resin A is a crosslinked isocyanate compound-epoxy compound.
• an isocyanate compound having a relatively low molecular weight and a highly reactive epoxy compound similarly having a relatively low molecular weight are penetrated into fibers, followed by a heat treatment, whereby a preferred fiber bundled body can be obtained.
• the compounds are crosslinked from the inside of a fiber bundle in this manner, single yarns are firmly adhered together inside the fiber bundle, and a firmly bundled fiber bundled body can be obtained.
• a blocked isocyanate having an aliphatic hexamethylene diisocyanate (HDI) structure which has excellent penetration into a fiber bundle
• a water-soluble high epoxy compound having a sorbitol polyglycidyl ether structure More specifically, it is preferable that dimethylpyrazole-blocked hexamethylene diisocyanate or caprolactam-blocked diphenylmethane diisocyanate is used as a blocked isocyanate, and a sorbitol polyglycidyl ether-type epoxy compound is used in combination as an epoxy compound.
• specific methods for attaching the resin A used as a bundling agent to the inside of a fiber bundled body are as follows.
• a multifilament (long fiber) formed of a collection of single fibers, a plurality of such fibers aligned, or long fibers in tow form are continuously fed from a bobbin or a beam creel. Then, (1) the fibers are impregnated in a tank containing the bundling agent, (2) the bundling agent is attached by a roller touch method, or (3) the bundling agent is sprayed and attached, for example.
• the method (1) in which the fibers are impregnated in a tank containing the bundling agent is preferable, and it is still more preferable that the amount attached is subsequently adjusted to a certain amount with a squeeze roller.
• a method in which the bundling agent is dispersed or dissolved in a water-based emulsion or an organic solvent, thus diluted, and used is preferable.
• An organic solvent having dissolved therein a bundling agent has increased viscosity, and its penetration into a fiber bundle tends to be insufficient.
• the fiber bundle having applied thereto a bundling agent is then subjected to a heat treatment to dry the dispersion medium for the bundling agent, or occasionally cause crosslinking by the heat treatment.
• a treatment device a contact hot roller and the like are usable.
• a non-contact hot-air drying furnace which prevents the bundling agent from adhering to or soiling the device and thus facilitates the work.
• the treatment temperature at this time is about 105 to 300° C., and it is particularly preferable that drying is performed at about 120 to 250° C.
• the obtained fibrous material is cut to a predetermined fiber length with a known cutting machine.
• the resin A is applied in an amount of 3 to 15 wt % relative to the total fiber weight.
• the amount attached is too small, it tends to happen that the bundle is released, and the single fibers come apart, resulting in loss of the fluidity of the material. This is because when a shear force is applied to fibers during kneading with concrete or mortar, the bundling of fibers with a bundling agent cannot be maintained. Meanwhile, in the case where the amount attached is too large, the strength of fibers tends not to be sufficiently utilized. In the case where the amount attached is increased too much, the cohesion itself is not much improved.
• the amount of the resin A attached relative to the fiber weight is more preferably 5.0 to 15.0 wt %, and particularly preferably within a range of 7.0 to 10.0 wt %.
• the fiber material for cement reinforcement of the invention is configured such that the resin A containing an isocyanate compound as a constituent component is present inside a fiber bundled body as described above, and it is further necessary that a resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body.
• a resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body.
• the isocyanate compound used as the resin A which has excellent affinity for water, has a relatively low molecular weight, and even at the time of crosslinking, the functional group reacts with water and is deactivated, causing no increase in the molecular weight.
• the cohesive strength tends to be insufficient.
• the amount of the resin A attached to the fiber bundle surface tends to be small, and the fiber bundle surface becomes flat, resulting in insufficient interfacial adhesion.
• the resin B containing an epoxy resin as a constituent component the interfacial adhesion strength with cement is increased.
• the resin B containing an epoxy resin as a constituent component should be a resin obtained by the reaction of a compound having an epoxy group as one of the constituent components. More specifically, as the resin B, as long as it is a resin obtained by the reaction of a compound having an epoxy group as one of the constituent components, any of those available as adhesives or coating materials in the open market may be used. However, a resin whose main component is a resin obtained by the reaction of a compound having an epoxy group as one of the constituent components is preferable. Further, in terms of cohesive strength and interfacial adhesion strength, an acrylic-modified epoxy resin and a bisphenol-A epoxy resin, which exhibit high performance, are preferable. It is particularly preferable that the resin B is a resin composed of an acrylic-modified bisphenol-A epoxy resin.
• an acrylic-modified epoxy resin is a resin having a high degree of acrylic modification, which is called an epoxy acrylate resin or a vinyl ester resin.
• This epoxy acrylate resin is a synthetic resin obtained by adding an acrylic group or a methacrylic group to an epoxy resin prepolymer, and is a resin resulting from the reaction between an epoxy resin and a (meth)acrylic acid.
• the resin has the same bisphenol skeleton as a bisphenol-A epoxy resin on the main chain and has an unsaturated ester group (vinyl ester group) on the side chain.
• the molecular weight of the resin B is 10,000 or more. Also in terms of the convenience of the processing treatment, it is preferable that the treatment liquid containing the resin B is a water-based emulsion.
• the resin B of the invention is used as a coating agent, for the purpose of improving strength and toughness or imparting heat resistance and chemical resistance, it is also preferable to add a known hardener, such as a melamine resin, a phenol resin, or a blocked isocyanate.
• a known hardener such as a melamine resin, a phenol resin, or a blocked isocyanate.
• the proportion of the hardener blended is not particularly limited, but it is preferable that the bisphenol-A or like epoxy resin, which is a base compound, is 50 wt % or more on a solid basis.
• the resin B is applied in an amount of 0.1 to 10 wt % relative to the total fiber weight.
• the amount attached is too small, when a stress is applied inside concrete or cement, the cohesive strength at the interface may be insufficient. Thus, it tends to happen that the fiber reinforcing material is easily shed and does not exhibit sufficient reinforcing properties.
• the amount attached is too large, the amount of the coating agent in the reinforcing material increases. Accordingly, due to an increase in the apparent fineness, the tensile strength of the fiber reinforcing material decreases, and the strength of the fiber tends not to be sufficiently utilized.
• the resin B is attached in an amount of 0.5 to 5.0 wt %, still more preferably within a range of 1.0 to 3.0 wt %. Further, it is particularly preferable that the total amount of the resins A and B attached to the fiber bundle is 8.0 to 15 wt %.
• the isocyanate compound contained in the resin A is a blocked isocyanate
• the resin B contains an acrylic-modified epoxy resin as a main component
• the resin B contains a bisphenol-A epoxy resin as a main component.
• the resin B contains an acrylic-modified bisphenol-A epoxy resin as a main component.
• the fiber material for cement reinforcement of the invention has become a fiber bundle having sufficient cohesion.
• the fiber material of the invention is suitable for use in cement mortar or concrete as described below.
• the reinforcing effect of the fibers decreases.
• unbundled single fibers are likely to be entangled with each other and form large fiber agglomerates, resulting in a decrease in the fresh fluidity or constructability of cement mortar or concrete.
• the fiber material for cement reinforcement of the invention has an excellent reinforcing effect and excellent constructability.
• high-strength or ultrahigh-strength mortar and concrete have been required. They generally have a low water/binder ratio, resulting in a high-viscosity material, whereby an even higher shear force is applied to the fiber material for reinforcement. For this reason, the fiber material of the invention with high cohesion is particularly useful.
• the fiber material for cement reinforcement of the invention is configured such that the resin A containing an isocyanate compound as a constituent component is present inside a fiber bundled body as described above, and the resin B containing an epoxy resin as a constituent component is present on a surface of the fiber bundled body. Then, the diameter of the bundled fiber reinforcing material and the fiber length of the fiber bundled body affect the bending toughness of a concrete or mortar formed body. That is, the presence of the fiber reinforcing material increases the bending fracture energy (sometimes referred to as “bending energy”) of a concrete or mortar formed body.
• the diameter of the bundled fiber reinforcing material is 0.05 to 1.0 mm, more preferably 0.1 mm to 0.8 mm, and still more preferably 0.3 mm to 0.5 mm. It is preferable that the length is 1 to 50 mm, more preferably 5 mm to 40 mm, and particularly preferably within a range of 15 mm to 35 mm.
• the impact on bending energy and fresh fluidity may also be considered from the aspect ratio expressed as the relation of the fiber length [mm]/the diameter of the fiber bundled body [mm]. It is preferable that the aspect ratio is 30 to 120, more preferably 50 to 80.
• the diameter of the bundled fiber reinforcing material is reduced, or the fiber length is increased, that is, when the aspect ratio is increased, the total contact surface area of the fibers with cement mortar or concrete increases, making it possible to increase the attachment strength. Further, it becomes possible to significantly improve the bending energy. However, meanwhile, when the aspect ratio is too high, an increased number of fibers break. As a result, when the width of cracks increases, the reinforcing effect decreases, and the bending energy tends to decrease. In addition, at the time of kneading in cement mortar or concrete, a high shear force is applied to the fibers, making it difficult to maintain the cohesion with the bundling agent. Further, in some cases, the bundle is released into single fibers, impairing the fluidity of the material.
• the diameter of the bundled fiber reinforcing material is increased, or the fiber length is reduced, that is, when the aspect ratio is reduced, the cutting of fibers is unlikely to occur, and the energy at the time of the shedding of fibers can be utilized at maximum.
• the fiber length of the bundled fiber is too short, or the diameter is too large, that is, when the aspect ratio is too low, the total contact surface area of the fibers with cement mortar or concrete is small, and it tends to be impossible to obtain a sufficient reinforcing effect.
• short fibers having a small fiber length are preferable, while in terms of improving the reinforcing effect, it is preferable to use short fibers having a large fiber length.
• the fiber length it is necessary to consider the deterioration of the workability due to a decrease in dispersibility or the generation of fiber agglomerates due to the entanglement of fibers during stirring, and it is preferable that the fiber length is within the above range.
• the diameter, the fiber length, and the like of the fiber bundled body are varied depending on the application, such as the case where the reinforcing effect within a narrow range where the crack width is less than 2 mm, etc., is expected, or the case where the reinforcing effect within a wide range, where the crack width is up to 6 mm, etc., is expected.
• this is affected by the attachment strength between each fiber bundled body and the concrete or mortar formed body, especially in a region having a small crack width, long fibers having a large aspect ratio, which have excellent adhesion strength, are effective.
• the concrete fiber material for reinforcement of the invention has high strength. More specifically, it is preferable that the tensile strength of the fiber bundled body forming the fiber material is 7 cN/dtex or more, particularly preferably within a range of 10 to 40 cN/dtex.
• the strength of the fiber material for reinforcement is measured after treatments with the resin A and the resin B and before cutting in the length direction.
• the tensile strength of the fiber material is too low, when a load is applied to cement mortar or concrete, the bending strength of the formed product tends to be low, or the impact strength tends to decrease.
• the incorporation rate of fibers forming the fiber material for reinforcement of the invention into cement mortar or concrete may be selected according to the purpose. However, it is usually preferable that the fibers are used within a range of 0.01 to 10.0 vol %, more preferably within a range of 0.05 to 5.0 vol %, still more preferably 0.1 to 3.0 vol %, and particularly preferably within a range of 0.2 to 1.5 vol %. Further, in another preferred mode, the fiber material for reinforcement of the invention and an existing fiber material are used in combination. In the case where the fiber incorporation rate is too low, the suppression of cracking and the impartment of strength and toughness tend to decrease.
• Vf fiber volume fraction
• the fiber material for reinforcement of the invention is particularly effective for cement serving as a binder for concrete or mortar, and is preferably used for concrete reinforcement and mortar reinforcement.
• Cement serving as a binder for concrete or mortar is selected considering the construction conditions of the worksite and the like, and the fiber material for cement reinforcement of the invention can be combined with various types of cement. More specifically, for example, various types of Portland cement such as ordinary cement, high-early-strength cement, ultrahigh-early-strength cement, low-heat cement, and moderate-heat cement, as well as various types of blended cement such as Portland blast furnace cement prepared by mixing these various types of Portland cement with fly ash, blast furnace slag, or the like, rapid hardening cement, and the like, can be mentioned. They can be used alone or as a mixture of two or more kinds.
• the fiber material for cement reinforcement of the invention is preferably used as a material for concrete or mortar together with the above cement (binder), and provides a concrete or mortar formed body containing the fiber material for cement reinforcement, which is another embodiment of the invention.
• admixtures binder
• admixtures include blast furnace slag powder, fly ash, silica fume, limestone powder, quartz powder, gypsum dihydrate, gypsum hemihydrate, gypsum anhydrite, quicklime-based expansive admixtures, and calcium sulfoaluminate-based expansive admixtures.
• Their proportions are not particularly limited, and various designs are possible.
• the following aggregates are added to the fiber material for cement reinforcement of the invention to form a concrete or mortar formed body containing aggregates.
• aggregates for concrete or mortar may only be fine aggregates, such as river sand, beach sand, mountain sand, crushed sand, silica sands Nos. 3 to 8, limestone, and slag fine aggregates.
• coarse aggregates such as river gravel, crushed stone, and artificial aggregates, are mixed with fine aggregates and used.
• the aggregate/cement (binder) ratio in concrete or mortar in terms of suppressing hydration heat, suppressing dry shrinkage, and reducing the cost, it is preferable that the aggregates are 50% or more.
• the fiber material for cement reinforcement of the invention causes a sufficient reinforcing effect even at a low fiber incorporation rate.
• the fiber material is particularly effective for concrete or mortar that has a low water/binder ratio, has a high coarse aggregate content, or has high material viscosity and is difficult to process. More specifically, it is preferable that the fiber material is used for a concrete or mortar formed body having a water/binder ratio of 45% or less, still more preferably 40% or less. Further, the fiber material is optimal for use in mortar or concrete having a water/binder ratio of 25% or less, or in mortar or concrete having a water/binder ratio of 45% or less and an aggregate/binder ratio of 250% or more.
• the fiber material for cement reinforcement of the invention can be preferably used in the case where the water/binder ratio is 25% or less, particularly preferably in the case of a water/binder ratio of 10 to 20%.
• the mechanical properties of the concrete or mortar obtained using cement having such a low water/binder ratio can be further enhanced.
• the fiber material of the invention may also be used with the water/binder ratio being normally high. However, when the water/binder ratio is too low, sufficient kneading is difficult even with the fiber material of the invention.
• a suitable amount of kneading water is added to cement and the like and kneaded. Then, it is preferable to employ a method for producing a concrete or mortar formed body containing the fiber material for cement reinforcement of the invention and having a water/binder ratio of 45% or less at the time of kneading.
• a method for producing a concrete or mortar formed body containing the fiber material for cement reinforcement of the invention and having a water/binder ratio of 45% or less at the time of kneading As the kneading water at this time, as long as components that adversely affect the hardening of cement and the like are not contained, tap water, underground water, river water, and like water can be used. However, it is preferable to use water conforming to “JIS A 5308, Appendix 9, Water Used for Kneading of Ready-Mixed Concrete.”
• cement mortar cement mortar
• sand fine particulate aggregates, fine aggregates
• cement and water are kneaded to paste-like softness, and the fiber material for cement reinforcement of the invention is mixed therewith.
• coarse aggregates coarse aggregates (gravel, etc.) are mixed.
• additives in addition to the above materials.
• additives include AE water reducing agents, high-range AE water reducing agents, shrinkage reducing agents, setting retarders, hardening accelerators, thickeners, defoaming agents, foaming agents, anti-corrosive agents, anti-freezing agents, clay mineral-based thixotropy-imparting agents, colorants, and water retention agents.
• the use of the fiber material for cement reinforcement of the invention has made it possible to obtain concrete or mortar having excellent physical properties.
• Specific examples of methods for adding the fiber material to concrete or mortar include a method in which cement, fine aggregates, coarse aggregates, and the like are previously mixed with the fiber material for cement reinforcement of the invention to form a dry premix, and then kneading water is added and kneaded, and also a method in which cement, fine aggregates, and coarse aggregates, and the like are sufficiently stirred with kneading water, and then the reinforcing material of the invention is finally added and kneaded.
• a kneading machine used for stirring the cement mortar or concrete containing the fiber material for reinforcement of the invention it is possible to use a pan-type mixer, a tilting mixer, an Omni mixer, a Hobart mixer, a truck mixer, or the like.
• the cohesion of fibers in the fiber material for cement reinforcement of the invention is high.
• kneading that causes a high shearing force such as the kneading of concrete or mortar having a low water/binder ratio
• breakage hardly occurred, and the fluidity and constructability of the material were not inhibited.
• fibers do not undergo rapid breakage even when the applied stress increases. As a result, the bending fracture energy of the formed product was significantly improved.
• the applications of such concrete or mortar formed bodies containing the fiber material for cement reinforcement of the invention are not particularly limited, and they can be widely used for general civil engineering and architectural applications. For example, by employing spray molding, press molding, vibration molding, centrifugation molding, and the like, wide variety of applications are possible, including the reinforcement of slopes, the foundation work of building structures, and the like. Further, also with respect to the production of secondary formed products (blocks, plate-like products, sheet-like products, tetrapods, etc.), various forming methods may be employed. In addition, in the case of mortar, in addition to use for the rough coating or finish coating of a concrete surface, it is also preferable to use the mortar for joints of bricks and concrete blocks, for example.
• Adjacent single yarns including single yarns located in the central part of the fiber bundle, are adhered together.
• Adjacent single yarns including single yarns located in the inner part (about 1 ⁇ 4 to 3 ⁇ 4 of the radius) of the fiber bundle, are adhered together.
• the obtained fiber reinforcing material was stirred with cement, aggregates, water, and the like by the method described in the following reference example, thereby giving ready-mixed concrete (or unhardened cement mortar).
• the following step was performed after the kneading step.
• the ready-mixed concrete was poured into a slump cone (conical post having a height of 15 cm, a bottom inner diameter of 10 cm, and a top inner diameter of 5 cm, with a hollow interior) while scraping off the excess, and the slump cone was slowly vertically pulled up.
• the ready-mixed concrete spreads in a circle over the aluminum board.
• the diameter of the spread circle at this time was measured as a flow value.
• the flow value reflects the fluidity of the ready-mixed concrete. When the flow value was 250 mm or more, the concrete was judged to have “excellent constructability”, while when it was less than 200 mm, the concrete was judged to have “poor constructability.” [0077]
• the ready-mixed concrete (or unhardened cement mortar) obtained in the reference example was used.
• a cylinder having a diameter of 100 mm was produced and then cured at 20° C. and 90% RH until a material age of 28 days, thereby giving a cylindrical test piece. Subsequently, measurement was performed in accordance with JIS A 1108 to determine the compressive strength.
• the ready-mixed concrete obtained in the reference example was placed in a mold 40 mm wide ⁇ 40 mm high ⁇ 160 mm long, and cured at 20° C. and 90% RH until a material age of 28 days, thereby giving a test piece for the measurement of bending fracture energy.
• the above test piece was subjected to a three-point bending test in accordance with JIS R 5201. More specifically, using a 10-t tensile compression tester (manufactured by Toyo Baldwin Corporation, “UNIVERSAL TESTING INSTRUMENT MODEL UTM 10 t”), the center of a 10-cm distance between support points was compressed at a rate of 2 mm/min. Then, from the measurement data of bending stress-strain obtained, the fracture energy necessary for the fracture of the test piece until a crack mouth opening displacement of 6 mm was calculated. A fracture energy of 10 kN/mm 2 or more was judged to be excellent, and a fracture energy of 10 kN/mm 2 or less was judged to be poor.
• each of the fiber reinforcing materials obtained in the examples and comparative examples was kneaded at a stirring rate of 140 rpm for about 3 minutes together with 1,000 g of low-heat Portland cement (manufactured by Taiheiyo Cement Corporation), 200 g of silica fume (manufactured by Elkem AS), 500 g of fine aggregates (manufactured by San-Ei Silica Co., Ltd., “Silica Sand No.
• each of the fiber reinforcing materials obtained in the examples and comparative examples was kneaded at a stirring rate of 140 rpm for about 3 minutes together with 450 g of low-heat Portland cement (manufactured by Taiheiyo Cement Corporation), 1,700 g of fine aggregates (manufactured by San-Ei Silica Co., Ltd., “Silica Sand No. 6”), 10 g of a high-range water reducing agent (“Rheobuild SP8HU” manufactured by BASF), and 170 g of water.
• unhardened cement mortar having a water/binder ratio of 40.0% and an aggregate/binder ratio of 380% was obtained.
• a copolymerized aramid fiber (copolymerized aromatic polyamide fiber, “Technora” manufactured by Teijin Limited, 1,670 dtex, the number of filaments: 1,000, tensile strength: 24.5 cN/dtex, “strength retention under conditions of 120° C., saturated water vapor, 100 hours: 99%”) was used.
• the fiber was single-twisted to give a fiber bundle having a twist coefficient of 2.
• a sorbitol polyglycidyl ether-based epoxy compound manufactured by Nagase ChemteX Corporation, “EX614B”
• dimethylpyrazole-blocked hexamethylene diisocyanate manufactured by Baxenden, “Trixene Aqua 201”, dimethylpyrazole block-HDI trimmer
• the obtained fiber bundle was immersed in the resin-A-containing liquid and then dried at a temperature of 200° C., thereby giving a fiber bundle having attached thereto a bundling agent at 10 wt %.
• an aqueous dispersion having a solid content of 10 w % and containing a carboxyl-group-containing acrylic-modified bisphenol-A epoxy resin (“DIC FINE EN” manufactured by DIC Corporation) was prepared.
• the fiber bundle having attached thereto the resin A was immersed in the aqueous dispersion of the resin B. Subsequently, the fiber bundle was dried at a temperature of 200° C., thereby giving a treated fiber bundle in which the amount of the coating agent (resin B) attached to the treated fiber bundle was 3 wt %. The diameter of the obtained treated fiber bundle was 0.45 mm. The treated fiber bundle was cut to 30 mm to give a fiber material for cement reinforcement. The physical properties are shown in Table 1.
• the ready-mixed concrete having a water/binder ratio of 19.2 of Reference Example 1 was cured, thereby giving a concrete formed body (the incorporation rate of the fiber material for reinforcement: 1 vol %).
• the evaluation results are shown in Table 1 (incidentally, some of the evaluation results are also shown in Table 2 for comparison).
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the resin component B to serve as a coating agent was changed from the acrylic-modified product used in Example 1 to a bisphenol-A epoxy resin (“jER” manufactured by Mitsubishi Chemical Corporation). The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the resin component A to serve as a bundling agent was changed from the dimethylpyrazole-blocked hexamethylene diisocyanate used in Example 1 to a mixed solution of a sorbitol polyglycidyl ether-based epoxy compound and caprolactam-blocked diphenylmethane diisocyanate (GRILBOND IL-6 manufactured by EMS) as the resin component A.
• GRILBOND IL-6 sorbitol polyglycidyl ether-based epoxy compound
• caprolactam-blocked diphenylmethane diisocyanate GRILBOND IL-6 manufactured by EMS
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that as the resin component A to serve as a bundling agent, the epoxy compound used in Example 1 was not used, and dimethylpyrazole-blocked hexamethylene diisocyanate was used alone. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that a urethane resin (“BONDIC HS770” manufactured by DIC Corporation) was used as the resin component A to serve as a bundling agent.
• a urethane resin (“BONDIC HS770” manufactured by DIC Corporation) was used as the resin component A to serve as a bundling agent. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the fiber used was changed from the copolymerized aramid fiber used in Example 1 to an aramid fiber made of a homopolymer (aromatic polyamide fiber, “Twaron” manufactured by Teijin Limited, 1,680 dtex, the number of filaments: 1,000, tensile strength: 20.8 cN/dtex).
• the results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the fiber used was changed from the copolymerized aramid fiber of Example 1 to a carbon fiber (“TENAX” manufactured by Toho Tenax Co., Ltd., 2,000 dtex, the number of filaments: 3,000, tensile strength: 15.0 cN/dtex). The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the fiber used was changed from the copolymerized aramid fiber having a total fineness of 1,670 dtex used in Example 1 to a fiber having a total fineness of 440 dtex (copolymerized aromatic polyamide fiber, “Technora” manufactured by Teijin Limited, 440 dtex, the number of filaments: 267), and the diameter of the treated reinforcing fiber material was 0.25 mm, which is about half. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the fiber used was changed from the treated reinforcing fiber material of Example 1 having a length of 30 mm to one having a length to 15 mm. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the fiber used was changed from the treated reinforcing fiber material of Example 1 having a length of 30 mm to one having a length to 35 mm. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the incorporation rate of the fiber material for cement reinforcement into a concrete formed body was changed from 1 vol % of Example 1 to 0.5 vol %. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the incorporation rate of the fiber material for cement reinforcement into a concrete formed body was changed from 1 vol % of Example 1 to 2.0 vol %. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the resin A to serve as a bundling agent was not used, and only the carboxyl-group-containing acrylic-modified bisphenol-A epoxy resin used as the coating agent resin B in Example 1 was used. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that the resin B to serve as a coating agent was not used, and only the sorbitol polyglycidyl ether-based epoxy compound and dimethylpyrazole-blocked hexamethylene diisocyanate, which are components blended as the bundling agent resin A in Example 1, were used. The results are also shown in Table 1.
• a fiber material for cement reinforcement and a concrete formed body were produced and evaluated in the same manner as in Example 1, except that in place of the resin A to serve as a bundling agent in Example 1, a sorbitol polyglycidyl ether-based epoxy compound was used alone without using a blocked isocyanate. The results are also shown in Table 1.
• the fiber used was changed from the copolymerized aramid fiber used in Example 1 to a PVA monofilament fiber (manufactured by Kuraray Co., Ltd., “RF 4000”, 4,000 dtex, the number of filaments: 1, tensile strength: 6.9 cN/dtex). Then, a concrete formed body was produced and evaluated in the same manner as in Example 1, except that this monofilament was used as a fiber material for cement reinforcement in place of a fiber bundled body. The results are also shown in Table 1 (incidentally, some of the evaluation results are also shown in Table 2 for comparison).
• the fiber material for cement reinforcement of the invention causes a smaller decrease in fluidity upon incorporation, and allows for construction in the same manner as in the case where no fibers are incorporated.
• high-durability concrete or mortar having excellent mechanical characteristics can be obtained.

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