WO2014157548A1 - Fibre de renforcement pour articles moulés hydrauliques, et matériau hydraulique contenant ladite fibre - Google Patents

Fibre de renforcement pour articles moulés hydrauliques, et matériau hydraulique contenant ladite fibre Download PDF

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Publication number
WO2014157548A1
WO2014157548A1 PCT/JP2014/058943 JP2014058943W WO2014157548A1 WO 2014157548 A1 WO2014157548 A1 WO 2014157548A1 JP 2014058943 W JP2014058943 W JP 2014058943W WO 2014157548 A1 WO2014157548 A1 WO 2014157548A1
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WIPO (PCT)
Prior art keywords
fiber
hydraulic
molded body
boric acid
alkali
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PCT/JP2014/058943
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English (en)
Japanese (ja)
Inventor
末森寿志
竹野入正利
井川淳之
竹本慎一
渡部俊一郎
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株式会社クラレ
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Publication of WO2014157548A1 publication Critical patent/WO2014157548A1/fr

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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
    • C04B14/42—Glass
    • C04B14/44—Treatment for enhancing alkali resistance
    • 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
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/107—Acids or salts thereof
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00586—Roofing materials
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00603—Ceiling materials
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction

Definitions

  • the present invention relates to a reinforcing fiber for a hydraulic molded body that has an excellent reinforcing effect on a molded body while maintaining the fluidity of a hydraulic material such as cement paste, mortar, concrete, and the like, and includes the reinforcing fiber.
  • the present invention relates to a hydraulic material used for forming a reinforcing molded body.
  • Hydraulic inorganic substances such as cement are widely used for the formation of hydraulic materials such as cement paste, mortar, concrete and the like. Hydraulic molded bodies formed from these hydraulic materials are widely used as civil engineering materials and building materials. It is known that a fibrous material is blended in a matrix of a hydraulic material such as concrete or cement mortar for the purpose of improving the performance such as bending strength and toughness of these molded bodies and suppressing cracks.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-1834773 discloses a bundled yarn in which a plurality of fibers are bundled with a water-soluble polymer resin, and the solution at pH 12 is used. A bundling yarn having a fineness of 50% or more is disclosed. With the method described in this document, it is possible to obtain a bundling yarn having a high reinforcing effect and a further excellent dispersibility, particularly a bundling yarn suitable for reinforcing a hydraulic cured product.
  • Patent Document 2 Japanese Patent Laid-Open No. 2012-25604
  • a) the total adhesion amount of the polycarboxylic acid ether anionic compound and the polyalkylene glycol is 0.5 to 20% based on the total fiber weight.
  • good fiber dispersibility can be obtained regardless of the kneading procedure of the raw material, the fluidity of the cement molded body when fresh (before solidification) is not impaired, and a high reinforcing effect is imparted. Can do.
  • Patent Document 1 it is possible to disperse the fibers satisfactorily and improve the reinforcing property of the molded body.
  • the fibers are uniformly dispersed in the cement paste, the fibers are solidified by the binding force of the fibers.
  • the fluidity of the previous cement paste fresh cement
  • Patent Document 2 although the fluidity of the hydraulic material before curing is improved, in order to obtain the effect, strict management of the moisture content of the reinforcing fiber is required. Poor sex.
  • An object of the present invention is to provide a reinforcing fiber for a hydraulic molded body that can achieve both the fluidity of the hydraulic material in a fresh state (uncured state) and the reinforcing property of the hydraulic molded body after curing. It is to provide.
  • Another object of the present invention is to provide a hydraulic material that includes such reinforcing fibers and a hydraulic inorganic substance and has excellent fluidity.
  • Still another object of the present invention is to provide a hydraulic molded body formed from such a hydraulic material and having excellent strength.
  • the inventors of the present invention have heretofore been considered to have a boric acid-containing compound that is highly reactive and has been considered to inhibit wettability between fiber and concrete by reacting with the fiber surface.
  • a boric acid-containing compound that is highly reactive and has been considered to inhibit wettability between fiber and concrete by reacting with the fiber surface.
  • the obtained cured product was found to be improved in strength by the reinforcing fiber, and the present invention was completed.
  • the first aspect of the present invention includes an alkali-resistant fiber and a boric acid-containing compound attached to the surface of the alkali-resistant fiber, and includes a hydraulic property containing 0.01 to 5% by mass of the boric acid-containing compound.
  • This is a reinforcing fiber for a molded body.
  • the boric acid-containing compound may be at least one compound selected from the group consisting of boric acid and two or more borate salts.
  • the boric acid-containing compound may be boric acid.
  • the alkali-resistant fiber may be at least one selected from the group consisting of alkali-resistant glass fiber, carbon fiber, polyvinyl alcohol fiber, polyethylene fiber, polypropylene fiber, acrylic fiber, and aramid fiber, for example.
  • Particularly preferred alkali-resistant fibers are polyvinyl alcohol fibers.
  • a polyvinyl alcohol fiber it is preferable to use a fiber produced by dry spinning or a fiber produced by wet spinning using an organic solvent.
  • the reinforcing fiber may have a fiber diameter of 10 to 1000 ⁇ m (preferably 100 to 900 ⁇ m), and a fiber aspect ratio of 30 to 500.
  • Such a reinforcing fiber may be, for example, a fiber having a boric acid-containing compound attached to an alkali-resistant fiber after spinning and drying.
  • a fiber having a boric acid-containing compound attached to an alkali-resistant fiber after spinning and drying may be, for example, a fiber having a boric acid-containing compound attached to an alkali-resistant fiber after spinning and drying.
  • it when it can be used in a dry state, it is possible to impart fluidity to the hydraulic material without adjusting the moisture content of the fibers.
  • the second aspect of the present invention is a hydraulic material including a hydraulic inorganic substance and the reinforcing fiber for hydraulic molded body.
  • the hydraulic inorganic substance may be made of cement.
  • the ratio F / C of the mass F of the reinforcing fiber to the mass C of the cement may be in the range of 1/300 to 100/1000.
  • the hydraulic material may further include an aggregate, and may include an admixture (an admixture other than reinforcing fibers). That is, the hydraulic material may further include at least one selected from fine aggregates, coarse aggregates, and admixtures (admixtures other than reinforcing fibers).
  • the hydraulic material may be a mixture of solid materials. Alternatively, the hydraulic material may be a water-containing mixture containing water (before curing).
  • the third aspect of the present invention includes a step of spinning or preparing an alkali-resistant fiber, a step of attaching a solution or dispersion of a boric acid-containing compound to the alkali-resistant fiber, and a solution or dispersion from the surface of the alkali-resistant fiber. And a step of drying and removing the solvent or dispersion medium of the dispersion.
  • the solution or dispersion of the boric acid-containing compound may be a solution or dispersion of at least one compound selected from the group consisting of boric acid and two or more borates.
  • a boric acid solution for example, an aqueous boric acid solution
  • a dispersion may be used.
  • a solution or dispersion of a boric acid-containing compound may be attached after stretching the spun alkali-resistant fiber.
  • the fibers may be cut after the boric acid-containing compound solution or dispersion is deposited.
  • the polyvinyl alcohol fiber when using a polyvinyl alcohol fiber as the alkali resistant fiber, in the above method, in the step of spinning the alkali resistant fiber, the polyvinyl alcohol fiber may be spun by dry spinning or wet spinning using an organic solvent.
  • a fourth aspect of the present invention is a method for forming a hydraulic molded body, comprising a hydraulic inorganic substance, the reinforcing fiber, water, and a fine aggregate, a coarse aggregate, and an admixture (if necessary) Kneading at least one kind selected from admixtures other than fibers) to form a hydraulic material comprising a water-containing mixture, forming the water-containing hard material to form a molded body, and the molded body Is a method for forming a hydraulic molded body.
  • both the fluidity of the hydraulic material in a fresh state and the reinforcing performance of the hydraulic molded body after curing can be achieved.
  • a hydraulic material including such a reinforcing fiber and a hydraulic material can be used without lowering its fluidity even though fibers are contained. Therefore, it is not necessary to increase the amount of water in order to ensure moldability, and a molded body having high compressive strength and fiber reinforced can be formed with high moldability.
  • the hydraulic molded body obtained by curing such a hydraulic material compared to a molded body formed from a hydraulic material that does not contain fibers, by fibers dispersed due to good fluidity, The bending strength can be improved.
  • the first embodiment of the present invention is a reinforcing fiber for a hydraulic molded body having an alkali-resistant fiber and a boric acid-containing compound attached to the surface of the alkali-resistant fiber.
  • the reinforcing fiber for hydraulic molded body may be substantially composed of an alkali-resistant fiber and a boric acid-containing compound.
  • the boric acid-containing compound adheres to the surface of the fiber, the surface portion has the highest boric acid (or boron) concentration even when the alkali-resistant fiber contains boron.
  • the alkali-resistant fiber used in the present invention is not particularly limited as long as it has chemical durability against alkali and is an organic fiber or an inorganic fiber.
  • Examples of the alkali-resistant inorganic fiber include alkali-resistant glass fiber, steel fiber (steel fiber), stainless fiber, and carbon fiber.
  • alkali-resistant organic fiber examples include polyvinyl alcohol (hereinafter sometimes referred to as PVA) fiber, polyolefin fiber (polyethylene fiber, polypropylene fiber, etc.), ultrahigh molecular weight polyethylene fiber, polyamide fiber (polyamide 6, Polyamide 6,6, polyamide 6,10, etc.), aramid fiber (particularly para-aramid fiber), polyparaphenylenebenzobisoxazole fiber (PBO fiber), acrylic fiber, rayon fiber (polynosic fiber, solvent-spun cellulose fiber, etc.), Examples include various alkali-resistant fibers such as polyphenylene sulfide fibers (PPS fibers) and polyether ether ketone fibers (PEEK fibers). These alkali resistant fibers may be used alone or in combination of two or more.
  • PPS fibers polyphenylene sulfide fibers
  • PEEK fibers polyether ether ketone fibers
  • alkali resistant glass fiber, carbon fiber, PVA fiber, polyolefin fiber (polyethylene fiber, polypropylene fiber, etc.), acrylic fiber, aramid fiber, etc. can be manufactured at low cost while having concrete reinforcement.
  • the alkali resistant fiber may be an organic fiber, for example, a polyolefin fiber (for example, polypropylene fiber) or a PVA fiber.
  • PVA fibers are particularly preferred as alkali-resistant fibers because they have not only good adhesion to cement but also excellent bonding with boric acid-containing compounds.
  • a PVA fiber As the alkali-resistant fiber, it is preferable to use a PVA fiber produced by dry spinning or a PVA fiber produced by wet spinning using an organic solvent.
  • boric acid-containing compound In the present invention, a boric acid-containing compound is adhered to the surface of the alkali-resistant fiber.
  • the boric acid-containing compound may be boric acid. Or a borate may be sufficient. Examples of the borate include sodium borate, potassium borate, and ammonium borate.
  • These boric acid-containing compounds may be used alone or in combination of two or more. For example, at least one (one or two or more) compounds selected from the group consisting of boric acid and two or more borates may be used.
  • the amount of the boric acid-containing compound is 0.01% by mass relative to the total fiber mass (in the case of a fiber consisting essentially of an alkali-resistant fiber and a boric acid-containing compound, the total mass of the alkali-resistant fiber and the boric acid-containing compound). Above, it is necessary that it is 5 mass% or less.
  • the amount of the boric acid-containing compound may be preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably less than 1% by mass. In addition, what is necessary is just to adjust the adhesion amount of a boric-acid containing compound so that it may become said range in the fiber of a dry state.
  • the adhesion amount of the boric acid-containing compound can be measured by, for example, an ICP method or a titration method using mannitol.
  • the fiber diameter of the reinforcing fiber for hydraulic molded body may be appropriately changed according to the use and purpose, and may be, for example, about 10 to 1000 ⁇ m, preferably about 100 to 900 ⁇ m, more preferably about 200 to 800 ⁇ m ( For example, it may be about 200 to 300 ⁇ m.
  • the fiber diameter of the alkali-resistant fiber may be in the above numerical range.
  • the reinforcing fiber for a hydraulic molded body of the present invention is usually used as a short fiber, and the fluidity of the hydraulic material is not suppressed by adhesion of a boric acid-containing compound, so that the fiber aspect ratio (fiber length / fiber diameter ratio) is It can be used in the state of small single fibers. Therefore, the aspect ratio of the fiber may be, for example, about 30 to 500, and preferably about 45 to 450. For example, the aspect ratio may be about 45 or more and about 100 or less. Essentially, the aspect ratio of the alkali-resistant fiber may be in the above range.
  • the fiber diameter can be measured by a known method.
  • the fiber diameter may be a numerical value calculated from the fineness of the fiber and the density of the fiber material (a diameter calculated assuming that the fiber cross section is a perfect circle).
  • the fineness of the fiber can be determined according to, for example, JIS L1015 “Testing method for chemical fiber staples (8.5.1)”.
  • the aspect ratio can be calculated from the fiber diameter and fiber length.
  • the reinforcing fiber is formed by spinning or spin-drying an alkali-resistant fiber and then attaching a solution or dispersion containing a boric acid-containing compound to the fiber. Thereafter, the solvent or dispersion medium is removed by drying from the fiber surface, whereby an alkali-resistant fiber having a boric acid-containing compound attached to the surface is obtained.
  • a solution or dispersion containing a boric acid-containing compound may be applied to the fiber using a roller or a spray.
  • the fiber may be immersed in a solution or dispersion containing a boric acid-containing compound to adhere the solution or dispersion to the fiber surface.
  • the adhesion treatment of the boric acid-containing compound may be performed on a fiber tow composed of a plurality of fibers.
  • the alkali resistant fiber may be stretched and / or cut as necessary after spinning and before attaching the boric acid-containing compound.
  • a solution or dispersion containing a boric acid-containing compound is attached to the fiber tow that has undergone a firing process.
  • Water or the like may be used as the solvent or dispersion medium. These liquids may contain various additives as necessary.
  • the fiber may be cut after attaching the boric acid-containing compound.
  • the boric acid-containing compound may be attached to the side surface, and may not be attached to the end surface (cross section).
  • the alkali-resistant fiber to which the boric acid-containing compound is attached can be further dried and used as necessary.
  • the moisture content may be, for example, less than 0.1% by mass relative to the total fiber weight.
  • conditions such as spinning and drawing that can obtain a predetermined fiber diameter, solvent that can obtain a predetermined amount of boric acid-containing compound, and concentration of dispersion medium are determined by preliminary tests. Manufacturing may be performed according to these conditions.
  • the aspect ratio of the fiber can be adjusted by cutting the fiber into a predetermined length corresponding to the fiber diameter.
  • PVA fiber When using a PVA fiber as the alkali-resistant fiber constituting the reinforcing fiber of the present invention, a PVA fiber having the following characteristics can be used.
  • the degree of polymerization of the PVA polymer constituting the PVA fiber is not particularly limited and can be appropriately selected according to the purpose, but it is an average obtained from the viscosity of the 30 ° C. aqueous solution in consideration of the mechanical properties of the resulting fiber.
  • the degree of polymerization may be about 500 to 20000 (preferably about 800 to 15000, more preferably about 1000 to 10,000).
  • the average degree of polymerization of the PVA-based polymer is preferably 1000 or more, more preferably 1200 or more, further preferably 1500 or more, and more preferably 1750 or more from the viewpoint of strength.
  • the PVA polymer may be a medium polymerization product having an average polymerization degree of 1000 or more and less than 3000, but may be a high polymerization product having an average polymerization degree of 3000 or more.
  • the saponification degree of the PVA polymer can be appropriately selected according to the purpose and is not particularly limited. However, from the viewpoint of the mechanical properties of the obtained fiber, for example, 95 mol% or more, more preferably 98 mol% or more. There may be.
  • the degree of saponification may be 99 mol% or more, or 99.8 mol% or more. If the saponification degree of the PVA polymer is too low, it is often not preferable in terms of mechanical properties, process passability, production cost, and the like of the obtained fiber.
  • the PVA fiber used in the present invention can be obtained by dissolving such a PVA polymer in a solvent, spinning it by any of wet, dry and wet methods, and dry-heat drawing.
  • Wet spinning is a method in which a spinning stock solution is discharged directly from a spinning nozzle to a solidification bath
  • dry-wet spinning is a method in which spinning stock solution is once discharged into air or inert gas at an arbitrary distance from the spinning nozzle. It is a method of discharging and then introducing into the solidification bath.
  • Dry spinning is a method of discharging a spinning solution into air or an inert gas.
  • the PVA fiber may be subjected to a stretching treatment as necessary after spinning. Moreover, the acetalization process etc. which are generally performed with the PVA-type fiber may be performed.
  • the solvent used for the spinning solution of the PVA fiber is not particularly limited as long as it is a solvent capable of dissolving PVA.
  • a solvent capable of dissolving PVA for example, water, dimethylsulfoxide (DMSO), dimethylformamide, dimethylacetamide, glycerin, ethylene glycol, trihydric alcohol such as triethylene glycol, or the like can be used alone or in combination.
  • DMSO dimethylsulfoxide
  • dimethylformamide dimethylacetamide
  • glycerin ethylene glycol
  • trihydric alcohol such as triethylene glycol, or the like
  • DMSO is particularly preferable from the viewpoint of availability and influence on the environmental load.
  • the polymer concentration in the spinning dope varies depending on the composition and degree of polymerization of the PVA polymer and the type of solvent, but is generally in the range of 6 to 60% by mass.
  • the above solvents can also be used in dry spinning. In that case, water or an organic solvent may be used.
  • the spinning dope includes a surfactant, an antioxidant, a decomposition inhibitor, an antifreezing agent, a pH adjusting agent, a concealing agent in addition to the PVA polymer, depending on the purpose.
  • Additives such as colorants and oils may be included.
  • the solvent used in the solidification bath can be appropriately selected according to the type of solvent used in the spinning dope.
  • the spinning dope is an aqueous solution
  • an aqueous solution of inorganic salts or sodium hydroxide having a solidification ability with respect to a PVA polymer such as sodium sulfate, ammonium sulfate, and sodium carbonate can be used.
  • the spinning dope is an organic solvent solution
  • the solidification bath has solidification ability for PVA polymers such as alcohols such as methanol, ethanol, propanol and butanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • Organic solvents can be used.
  • a fiber obtained by dry spinning or a fiber obtained by wet spinning from a spinning stock solution using an organic solvent as a solvent is preferable from the viewpoint of fiber strength.
  • the fiber In order to extract and remove the solvent of the spinning dope from the solidified yarn, it may be passed through an extraction bath, or the yarn may be wet-drawn simultaneously with the extraction. Further, after wet stretching, the fiber may be dried, and if necessary, dry heat stretching may be performed. When stretching, the total stretching ratio (product of wet stretching and stretching ratio after drying) may be, for example, 5 to 25 times, preferably about 8 to 20 times.
  • the hydraulic material according to the second embodiment of the present invention is a hydraulic material including a hydraulic inorganic substance and the reinforcing fibers described in the first embodiment. Such a material can be used to form a hydraulic molded body reinforced with fibers.
  • the hydraulic material include a composition containing cement and a gypsum composition containing gypsum.
  • the hydraulic material containing cement include cement paste, mortar, and concrete.
  • Cement paste is a composition containing cement and water
  • mortar is a composition containing cement, water and fine aggregate
  • concrete (fresh concrete) is usually cement, water, fine aggregate and coarse bone. It is a composition containing a material.
  • compositions contain various admixtures (admixtures / admixtures) as necessary, and in the present invention, reinforcing fibers are included.
  • a cement composition, a mortar composition, and a concrete composition composed of a mixture of solids before the addition of water can also be cited as the hydraulic material according to the present invention.
  • a hydraulic material containing water such as cement paste, mortar, concrete, or the like can be formed.
  • Examples of hydraulic inorganic substances contained in hydraulic materials include cement and gypsum.
  • Examples of the cement (hydraulic cement) include ordinary Portland cement, early-strength Portland cement, low heat cement, medium temperature heat Portland cement and other Portland cement, alumina cement, blast furnace cement, silica cement, fly ash cement, eco cement, and the like. It is done.
  • Examples of gypsum include dihydrate gypsum, ⁇ -type or ⁇ -type hemihydrate gypsum, and anhydrous gypsum.
  • These hydraulic inorganic substances may be used alone or in combination of two or more. These hydraulic inorganic substances are usually used in a powder (fine particle) state, and react with the added water to condense and harden the hydraulic material.
  • the hydraulic material may contain various aggregates as necessary. Examples of such aggregates include fine aggregates and coarse aggregates. These aggregates may be used alone or in combination of two or more.
  • the fine aggregate examples include fine particles having a particle size of 5 mm or less. As long as it satisfies such a particle size, it is not particularly limited.
  • materials used as fine aggregates include river sand, mountain sand, sea sand, crushed sand, quartz sand, slag, glass sand, iron sand, ash sand, carbonic acid
  • sands such as calcium and artificial sand.
  • the coarse aggregate is an aggregate containing 85% or more by weight% of particles having a particle diameter of 5 mm or more.
  • the coarse aggregate may be composed of particles having a particle size of more than 5 mm.
  • various gravels, artificial aggregates (such as blast furnace slag), recycled aggregates (such as recycled aggregates of building waste), and the like can be used.
  • the above-mentioned aggregate may include a lightweight aggregate.
  • lightweight aggregates include natural lightweight aggregates such as volcanic gravel, expanded slag and charcoal, and artificial lightweight aggregates such as foamed pearlite, foamed perlite, foamed black stone, vermiculite, and shirasu balloon.
  • the admixture is a substance mixed in the hydraulic material in addition to the hydraulic inorganic substance, water, and aggregate.
  • the admixture include admixtures such as silica fume, fly ash, blast furnace slag fine powder, limestone powder, quartz powder, AE agent, fluidizing agent, water reducing agent, high performance water reducing agent, AE water reducing agent, high performance AE.
  • admixtures include a water reducing agent, a thickening agent, a water retention agent, a water repellent, a swelling agent, a curing accelerator and a setting retarder.
  • the blending amount of the reinforcing fiber, hydraulic inorganic substance, aggregate, admixture, etc. and the amount of water added can be appropriately adjusted according to the desired molded article. You may use a well-known compounding quantity suitably.
  • the reinforcing fiber for hydraulic molded body used in the present invention can impart high fluidity to the hydraulic material by the function of the fiber itself, the amount of use of a fluidizing agent is reduced, and the hydraulic property is reduced. The strength of the molded body can be improved.
  • reinforcing fibers are mixed with the hydraulic material.
  • the reinforcing fibers those described in the description of the first embodiment can be used.
  • the water cement ratio (W / C) may be about 15 to 60%, preferably 18 to 80, where W is the mass of water and C is the mass of cement. It may be 40%, more preferably 20-30%.
  • the flow value may be about 175 to 300 mm, more preferably about 180 to 250 mm. It may be. This flow value can be obtained by the flow test method described in the physical test method of JIS R 5201 cement.
  • a molded body can be obtained by curing the hydraulic material.
  • a hydraulic molded body is molded after being molded into a desired form using a hydraulic material, and can be used as various construction materials and civil engineering materials.
  • construction materials for example, foundations of building structures, roofing materials, exterior wall materials, partitions, ceiling materials, etc.
  • civil engineering materials for example, bridges, expressways, tunnels, slope reinforcements
  • Tetrapot etc.
  • the forming step of the hydraulic material and the hardening step of the formed hydraulic material can be performed according to a known method.
  • the bulk density of the hydraulic molded body was calculated by the following equation by measuring the weight of a prismatic test piece having a cross section of 40 mm ⁇ 40 mm and a length of 160 mm prepared for the above-described bending strength measurement test.
  • Bulk density (g / cm 3 ) Specimen weight (g) ⁇ Specimen volume (cm 3 )
  • the volume of the test piece was calculated as 256 cm 3 .
  • the adhesion amount of the boric acid-containing compound was measured by a mannitol method by titration.
  • boric acid on the fiber surface is dissolved in water, mannitol (mannit) that easily reacts with boron is added, the amount of boric acid-containing compound is determined by titration with NaOH, and boron adhering to the fiber surface is obtained.
  • the amount of acid-containing compound was quantified.
  • Example 1 PVA with a polymer polymerization degree of 1750 and a saponification degree of 99.9 mol% is dissolved in DMSO so that the PVA concentration is 21% by mass to form a spinning stock solution, and wet spinning using a mixed solvent of methanol and DMSO as a solidification bath. Spun in. Further, DMSO was extracted with methanol, followed by wet stretching and drying, followed by dry heat stretching (stretching temperature 230 ° C., total stretching ratio 13 times). A boric acid aqueous solution (boric acid concentration: 3 g / L) was attached to the surface by roller touch on the stretched PVA fiber, and then dried to attach boric acid to the PVA fiber.
  • boric acid-attached PVA fiber having a fiber diameter of 250 ⁇ m and an aspect ratio of 60.
  • the amount of boric acid adhered to the fiber was calculated based on titration by the mannitol method using mannitol manufactured by Kanto Chemical Co., Inc.
  • Hobart mixer with a maximum capacity of 20L, 600 parts by weight of ordinary cement (manufactured by Taiheiyo Cement Co., Ltd.), 400 parts by weight of silica fume (manufactured by EFACO), 900 parts by weight of fine aggregate (No.
  • 6.5 cinnabar maximum diameter of about 1 mm
  • 150 parts by weight of water, 25 parts by weight of polycarboxylic acid-based high-performance AE water reducing agent (“SSP-104” manufactured by Takemoto Yushi Co., Ltd.) are kneaded for 12 minutes in a volume of about 2 L, and the finished plain mortar
  • a fiber-reinforced mortar was prepared as a hydraulic material by adding 35 parts by weight of the fiber and additional kneading for 2 minutes.
  • this mortar was poured into a prismatic mold with a cross section of 40 mm x 40 mm and a length of 160 mm, then sealed and cured in a room at 20 ° C for 48 hours, wrapped in a compress, and heated at a temperature of 90 ° C.
  • the molded body test piece was produced by curing with heat and humidity in a constant temperature and humidity chamber with a humidity of 98%, and the bulk density of the molded body was calculated from the weight and volume, and then subjected to a bending strength test.
  • the mortar was subjected to a flow test using the method described in the physical test method of JIS R 5201 cement to obtain a 15-stroke flow value.
  • the zero stroke flow value was determined according to the above method for the case where no falling motion was given.
  • Table 1 shows the boric acid adhesion amount of the fiber, the flow value of the mortar, the compression strength of the molded body, the bending strength (maximum yield strength) of the molded body, and the bulk density of the molded body.
  • Example 2 A PVA fiber, a hydraulic material, and a hydraulic molded body were produced in the same manner as in Example 1 except that the amount of boric acid attached to the alkali-resistant fiber was changed to the composition shown in Table 1.
  • Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 6 A PVA-based fiber, a hydraulic material, and a hydraulic molded body were produced in the same manner as in Example 1 except that the fiber diameter was 300 ⁇ m, the aspect ratio was 50, and the boric acid adhesion amount was 0.3 mass%. Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 7 A PVA-based fiber, a hydraulic material, and a hydraulic molded body were produced in the same manner as in Example 1 except that the aspect ratio of the fiber was 48 and the boric acid adhesion amount was 0.3% by mass. Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 8 Polypropylene (PP) fibers were prepared, and an aqueous boric acid solution was applied by roller touch, and then cut to obtain boric acid-attached PP fibers having a fiber diameter of 250 ⁇ m and an aspect ratio of 60. The boric acid adhesion measured by the mannitol method was 0.3% by mass.
  • a hydraulic material (mortar) was prepared in the same manner as in Example 1 except that this fiber was used, and the flow value of the hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body were determined. The results are shown in Table 1.
  • Example 1 A PVA fiber, a hydraulic material and a hydraulic molded body were produced in the same manner as in Example 1 except that PVA fiber was obtained without adhering boric acid. Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 2 A PVA fiber, a hydraulic material, and a hydraulic molded body were produced in the same manner as in Example 1 except that the amount of boric acid attached to the alkali-resistant fiber was changed to the composition shown in Table 1.
  • Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 3 A PVA-based fiber, a hydraulic material, and a hydraulic molded body were produced in the same manner as in Example 1 except that the amount of boric acid adhered was 6% by mass. Table 1 shows the flow value of the obtained hydraulic material and the compressive strength, maximum proof stress and bulk density of the hydraulic molded body.
  • Example 4 In the same manner as the plain mortar before fiber addition in Example 1, a mortar containing no reinforcing fiber was produced. Using this mortar, in the same manner as in Example 1, the flow value, the bulk density, the measurement of the compact compression strength, and the bending strength test were performed. The results are shown in Table 1. In the bending strength test, after reaching the proportional limit strength (LOP), the molded body broke and the maximum proof stress measured in the plastic deformation region of the molded body could not be detected.
  • LOP proportional limit strength
  • each of Examples 1 to 7 has a high 0-stroke flow value and 15-stroke flow value indicating the fluidity of the hydraulic material, and the resulting molded article has a high compressive strength. The value is shown.
  • the high bulk density shown in Examples 1 to 7 also indicates that the hydraulic material has good fluidity, and as a result, a dense molded body was formed.
  • Example 8 shows, even when boric acid is adhered to reinforcing fibers other than PVA in an amount within the range specified in the present invention, the fluidity of the hydraulic material is increased and the compression strength of the molded body is increased. The effect of maintaining a high value was confirmed.
  • Comparative Example 1 in which boric acid is not adhered to the fiber, the fluidity of the hydraulic material is lowered as shown by the 0-stroke flow value and the 15-stroke flow value, so that workability is inferior. Further, the bulk density of the molded body was lower than those of Examples 1 to 7, indicating that the void volume ratio was increased due to the decrease in the flowability of the mortar. Moreover, even if it is a very small amount of boric acid, as shown in Comparative Example 2, the effect of adhering boric acid is not seen, and the same result as Comparative Example 1 is shown.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention concerne une fibre de renforcement pour articles moulés hydrauliques, qui comprend une fibre résistant aux alcalis et un composé contenant de l'acide borique fixé sur la surface de la fibre, le composé contenant de l'acide borique étant contenu en une quantité de 0,01 à 5 % en masse, et un matériau hydraulique qui comprend une substance inorganique hydraulique et la fibre de renforcement pour des articles moulés hydrauliques.
PCT/JP2014/058943 2013-03-29 2014-03-27 Fibre de renforcement pour articles moulés hydrauliques, et matériau hydraulique contenant ladite fibre WO2014157548A1 (fr)

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CN105585266A (zh) * 2014-10-24 2016-05-18 深圳市维特耐新材料有限公司 一种水泥基复合材料用有机复合纤维及其生产方法

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JP6390411B2 (ja) * 2014-12-18 2018-09-19 宇部興産株式会社 既存橋脚の補強方法、補強橋脚の製造方法、ポリマーセメントモルタル、及び補強橋脚
JP6390410B2 (ja) * 2014-12-18 2018-09-19 宇部興産株式会社 既存橋脚の補強方法、補強橋脚の製造方法、ポリマーセメントモルタル、及び補強橋脚
JP2016124724A (ja) * 2014-12-26 2016-07-11 株式会社クラレ 水硬性成形体用補強繊維およびこの補強繊維を含む水硬性材料

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JP2004511421A (ja) * 2000-10-17 2004-04-15 ジェイムズ　ハーディー　リサーチ　ピーティーワイ．リミテッド 殺生物剤で処理した耐久性あるセルロース繊維を使用した、繊維セメント複合材料
JP2009108432A (ja) * 2007-10-29 2009-05-21 Kuraray Co Ltd ポリビニルアルコール系繊維およびその製造方法

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JPS56125266A (en) * 1980-03-06 1981-10-01 Kuraray Co Fiber reinforced cement material
JPH04228610A (ja) * 1990-10-18 1992-08-18 Kuraray Co Ltd ポリビニルアルコール系合成繊維及びその製造方法

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JP2004511421A (ja) * 2000-10-17 2004-04-15 ジェイムズ　ハーディー　リサーチ　ピーティーワイ．リミテッド 殺生物剤で処理した耐久性あるセルロース繊維を使用した、繊維セメント複合材料
JP2009108432A (ja) * 2007-10-29 2009-05-21 Kuraray Co Ltd ポリビニルアルコール系繊維およびその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105585266A (zh) * 2014-10-24 2016-05-18 深圳市维特耐新材料有限公司 一种水泥基复合材料用有机复合纤维及其生产方法

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