JP6302716B2 - Reinforcing fiber for hydraulic molded body and hydraulic material containing the same - Google Patents
Reinforcing fiber for hydraulic molded body and hydraulic material containing the same Download PDFInfo
- Publication number
- JP6302716B2 JP6302716B2 JP2014065549A JP2014065549A JP6302716B2 JP 6302716 B2 JP6302716 B2 JP 6302716B2 JP 2014065549 A JP2014065549 A JP 2014065549A JP 2014065549 A JP2014065549 A JP 2014065549A JP 6302716 B2 JP6302716 B2 JP 6302716B2
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- JP
- Japan
- Prior art keywords
- fiber
- hydraulic
- molded body
- boric acid
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims description 94
- 239000012783 reinforcing fiber Substances 0.000 title claims description 56
- 239000000835 fiber Substances 0.000 claims description 210
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 74
- 239000004327 boric acid Substances 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 49
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 49
- 239000003513 alkali Substances 0.000 claims description 48
- 239000004568 cement Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000009987 spinning Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000002166 wet spinning Methods 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 238000000578 dry spinning Methods 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000002612 dispersion medium Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002972 Acrylic fiber Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims 1
- 235000010338 boric acid Nutrition 0.000 description 70
- 229960002645 boric acid Drugs 0.000 description 70
- 239000004570 mortar (masonry) Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 238000005452 bending Methods 0.000 description 15
- 239000004567 concrete Substances 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000003014 reinforcing effect Effects 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 229930195725 Mannitol Natural products 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000000594 mannitol Substances 0.000 description 6
- 235000010355 mannitol Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000006072 paste Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 239000004035 construction material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Textile Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本発明は、セメントペースト、モルタル、コンクリートなどの水硬性材料の流動性を維持しつつ、成形体に対して優れた補強効果を有する水硬性成形体用補強繊維、およびこの補強繊維を含み、繊維補強成形体の形成に用いられる水硬性材料に関する。 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.
セメント等の水硬性無機物質は、例えば、セメントペースト、モルタル、コンクリート等の水硬性材料の形成に広く用いられている。これらの水硬性材料から形成される水硬性成形体は、土木資材、建築資材として、広く使用されている。これらの成形体の曲げ強度、靭性等の性能の改善やひび割れ抑制を目的として、コンクリート、セメントモルタルなどの水硬性材料のマトリックスに繊維状物を配合することが知られている。 Hydraulic inorganic substances such as cement are widely used for forming 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.
しかしながら、繊維をマトリックス中に均一に分散することは極めて困難であり、混練の際に繊維が絡まって塊状物（ファイバーボール）となり、補強効果が発揮されにくい問題がある。そのような問題を改善するために、例えば、特許文献１（特開平１０−１８３４７３号公報）には、複数本の繊維が水溶性高分子樹脂で集束された集束糸であって、ｐＨ１２における解繊度５０％以上であることを特徴とする集束糸が開示されている。この文献に記載の方法では、補強効果が高く、より一層分散性に優れた集束糸、特に水硬性硬化物の補強に好適な集束糸を得ることができる。 However, it is extremely difficult to disperse the fibers uniformly in the matrix, and there is a problem that the reinforcing effect is difficult to be exhibited because the fibers are entangled into a lump (fiber ball) during kneading. In order to improve such a problem, for example, Patent Document 1 (Japanese Patent Laid-Open No. 10-183473) discloses a bundled yarn in which a plurality of fibers are bundled with a water-soluble polymer resin, and a 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.
また、特許文献２（特開２０１２−２５６０４号公報）には、ａ）ポリカルボン酸エーテル系アニオン性化合物とポリアルキレングリコールの合計付着量が全繊維重量に対して０．５〜２０％であること、およびｂ）水分付着量が全繊維重量に対して０．５〜２０％であることを満足するセメント成形体補強用短繊維が開示されている。この文献に記載の方法では、原料の混練手順に関わらず良好な繊維分散性が得られ、セメント成形体のフレッシュ時（固化前）の流動性を損わず、かつ高い補強効果を付与することができる。 Further, in Patent Document 2 (Japanese Patent Laid-Open No. 2012-25604), a) The total adhesion amount of the polycarboxylic acid ether-based anionic compound and the polyalkylene glycol is 0.5 to 20% with respect to the total fiber weight. And b) a short fiber for reinforcing a cement molded body satisfying that the moisture adhesion amount is 0.5 to 20% with respect to the total fiber weight. In the method described in this document, 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.
しかしながら、特許文献１の技術では、繊維が良好に分散し、成形体の補強性を向上することは可能であるが、セメントペースト中で繊維が均一に分散したとしても、繊維の拘束力によって固化前のセメントペースト（フレッシュセメント）の流動性が著しく低下する。一方、特許文献２の技術では、硬化前の水硬性材料の流動性は改善されるものの、その効果を得るためには、補強繊維の水分量の厳密な管理が求められるため、使用上の簡便性に乏しい。 However, with the technique of Patent Document 1, it is possible to disperse the fibers satisfactorily and improve the reinforcing property of the molded body. However, even if 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) is significantly reduced. On the other hand, in the technique of 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.
本発明の目的は、フレッシュな状態（未硬化の状態）での水硬性材料の流動性と、硬化後の水硬性成形体の補強性とを両立することができる水硬性成形体用補強繊維を提供することにある。
本発明の別の目的は、このような補強繊維と水硬性無機物質とを含み、流動性に優れる水硬性材料を提供することにある。
本発明のさらに別の目的は、このような水硬性材料から形成され、優れた強度を有する水硬性成形体を提供することにある。
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.
本発明の発明者らは、上記目的を達成するために鋭意検討した結果、従来、反応性が高く繊維表面と反応して繊維とコンクリートとの濡れ性を阻害するとみなされていたホウ酸含有化合物は、驚くべきことに、特定のわずかな量を繊維表面に付着させると、補強繊維が混和された成形体材料（水硬性材料）のフレッシュな状態での流動性を維持することが可能であり、さらに得られた硬化物は補強繊維によりその強度が向上されることを見出し、本発明を完成した。 As a result of diligent studies to achieve the above object, 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. Surprisingly, it is possible to maintain the fluidity of the molded material (hydraulic material) mixed with the reinforcing fibers in a fresh state when a small amount is attached to the fiber surface. Further, the obtained cured product was found to be improved in strength by the reinforcing fiber, and the present invention was completed.
すなわち、本発明の第１の態様は、耐アルカリ性繊維と、前記耐アルカリ性繊維の表面に付着したホウ酸含有化合物とを有し、前記ホウ酸含有化合物を０．０１〜５質量％含む水硬性成形体用補強繊維である。
上記補強繊維において、前記ホウ酸含有化合物は、ホウ酸および二種以上のホウ酸塩からなる群から選択される少なくとも一種の化合物であってもよい。例えば、前記ホウ酸含有化合物は、ホウ酸であってもよい。
That is, the first aspect of the present invention is a hydraulic property comprising an alkali-resistant fiber and a boric acid-containing compound attached to the surface of the alkali-resistant fiber, and containing 0.01 to 5% by mass of the boric acid-containing compound. This is a reinforcing fiber for a molded body.
In the reinforcing fiber, 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. For example, the boric acid-containing compound may be boric acid.
前記耐アルカリ性繊維は、例えば耐アルカリ性ガラス繊維、炭素繊維、ポリビニルアルコール系繊維、ポリエチレン繊維、ポリプロピレン繊維、アクリル繊維、及びアラミド繊維からなる群から選択される少なくとも一種であってもよい。特に好ましい耐アルカリ性繊維は、ポリビニルアルコール系繊維である。ポリビニルアルコール系繊維を用いる場合、乾式紡糸により作製した繊維、または有機溶媒を用いた湿式紡糸により作製した繊維を用いることが好ましい。 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. When using 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.
また、前記補強繊維は、繊維径が１０〜１０００μｍ（好ましくは１００〜９００μｍ）であり、かつ繊維のアスペクト比が３０〜５００であってもよい。 The reinforcing fiber may have a fiber diameter of 10 to 1000 μm (preferably 100 to 900 μm) and a fiber aspect ratio of 30 to 500.
このような補強繊維は、例えば、紡糸乾燥後の耐アルカリ性繊維に対して、ホウ酸含有化合物が付着した繊維であってもよい。また、乾燥状態で用いることが可能である場合、繊維の水分調整などを行なわなくとも、水硬性材料に流動性を与えることが可能である。 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. In addition, 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.
本発明の第２の態様は、水硬性無機物質と、前記水硬性成形体用補強繊維と、を含む水硬性材料である。 The 2nd aspect of this invention is a hydraulic material containing a hydraulic inorganic substance and the said reinforcement fiber for hydraulic molded objects.
上記水硬性材料において、前記水硬性無機物質は、セメントからなるものであってもよい。この場合、セメントの質量Ｃに対する補強繊維の質量Ｆの比Ｆ/Ｃは、１/３００〜１００/１０００の範囲にあってもよい。
上記水硬性材料は、さらに骨材を含んでもよく、混和材料（補強繊維以外の混和材料）を含んでもよい。すなわち、上記水硬性材料は、さらに細骨材、粗骨材、混和材料（補強繊維以外の混和材料）から選択される少なくとも一種を含むものであってもよい。
上記水硬性材料は、固体材料の混合物であってもよい。あるいは、上記水硬性材料は、水を含む（硬化前の）含水混合物であってもよい。
In the hydraulic material, the hydraulic inorganic substance may be made of cement. In this case, 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).
本発明の第３の態様は、耐アルカリ性繊維を紡糸または準備する工程と、前記耐アルカリ性繊維にホウ酸含有化合物の溶液または分散液を付着させる工程と、前記耐アルカリ性繊維の表面から前記溶液または分散液の溶媒または分散媒を乾燥除去する工程とを含む、水硬性成形体用補強繊維の製造方法である。この製造方法により、上記の補強繊維を製造することができる。
上記製造方法において、ホウ酸含有化合物の溶液または分散液は、ホウ酸および二種以上のホウ酸塩からなる群から選択される少なくとも一種の化合物の溶液または分散液であってもよい。例えば、ホウ酸の溶液（例えば、ホウ酸水溶液）または分散液を用いてもよい。
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. With this manufacturing method, the above-described reinforcing fiber can be manufactured.
In the above production method, 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. For example, a boric acid solution (for example, an aqueous boric acid solution) or a dispersion may be used.
上記の方法において、紡糸した耐アルカリ性繊維を延伸後、ホウ酸含有化合物の溶液または分散液を付着させてもよい。ホウ酸含有化合物の溶液または分散液を付着させた後、繊維を切断してもよい。 In the above method, 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.
耐アルカリ性繊維としてポリビニルアルコール系繊維を用いる場合、上記の方法において、耐アルカリ性繊維を紡糸する工程では、乾式紡糸、または有機溶媒を用いた湿式紡糸により、ポリビニルアルコール系繊維を紡糸してもよい。 When using a polyvinyl alcohol fiber as the alkali resistant fiber, in the method described above, 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.
本発明の第４の態様は、水硬性成形体の形成方法であって、水硬性無機物質と、上記補強繊維と、水と、必要に応じ細骨材、粗骨材、混和材料（前記補強繊維以外の混和材料）から選択される少なくとも一種とを練り混ぜて、含水混合物からなる水硬性材料を形成する工程と、前記含水硬性材料を成形して成形体を形成する工程と、前記成形体を硬化する工程とを含む、水硬性成形体の形成方法である。 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.
本発明の水硬性成形体用補強繊維では、フレッシュな状態の水硬性材料の流動性と、硬化後の水硬性成形体の補強性とを両立することができる。
また、このような補強繊維と水硬性材料とを含む水硬性性材料は、繊維が入っているにもかかわらずその流動性を低下させずに用いることができる。従って、成形性を確保するために水分量を増加させる必要がなく、圧縮強度が高く、かつ繊維補強された成形体を高い成形性で形成することができる。
さらに、このような水硬性材料が硬化して得られた水硬性成形体は、良好な流動性に起因して分散した繊維によって、繊維を含まない水硬性材料から形成された成形体に比べ、その曲げ強度を向上することができる。
In the reinforcing fiber for a hydraulic molded body of the present invention, 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.
In addition, 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.
Furthermore, 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.
［水硬性成形体用補強繊維］
本発明の第１の実施形態は、耐アルカリ性繊維と、前記耐アルカリ性繊維の表面に付着したホウ酸含有化合物とを有する水硬性成形体用補強繊維である。
この水硬性成形体用補強繊維は、実質的に、耐アルカリ性繊維と、ホウ酸含有化合物からなるものであってもよい。
本発明においては、繊維の表面にホウ酸含有化合物が付着しているため、耐アルカリ性繊維がホウ素を含有する場合であっても、ホウ酸（あるいはホウ素）濃度は表面部分が最も高くなる。
[Reinforcing fiber for hydraulic molded body]
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.
In the present invention, since 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.
（耐アルカリ性繊維）
本発明で用いられる耐アルカリ性繊維は、アルカリに対する化学的な耐久性を有する限り、有機繊維であっても無機繊維であっても特に限定されない。例えば、耐アルカリ性無機繊維としては、耐アルカリ性ガラス繊維、鋼繊維（スチールファイバー）、ステンレスファイバー、炭素繊維などが挙げられる。また、耐アルカリ性有機繊維としては、ポリビニルアルコール（以下、ＰＶＡと称することがある）系繊維、ポリオレフィン系繊維（ポリエチレン繊維、ポリプロピレン繊維、など）、超高分子量ポリエチレン繊維、ポリアミド系繊維（ポリアミド６、ポリアミド６，６、ポリアミド６，１０など）、アラミド繊維（特にパラアラミド繊維）、ポリパラフェニレンベンゾビスオキサゾール系繊維（ＰＢＯ繊維）、アクリル繊維、レーヨン系繊維（ポリノジック繊維、溶剤紡糸セルロース繊維等）、ポリフェニレンサルファイド繊維（ＰＰＳ繊維）、ポリエーテルエーテルケトン繊維（ＰＥＥＫ繊維）、等の各種耐アルカリ性繊維などが挙げられる。これらの耐アルカリ性繊維は、単独でまたは二種以上組み合わせて使用してもよい。
(Alkali resistant fiber)
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. Examples of the alkali-resistant organic fiber 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.
これらのうち、耐アルカリ性ガラス繊維、炭素繊維、ＰＶＡ系繊維、ポリオレフィン系繊維（ポリエチレン繊維、ポリプロピレン繊維など）、アクリル繊維、アラミド繊維などが、コンクリート補強性を有しつつ、低コストで製造できる観点から有利に使用できる。
耐アルカリ性繊維は、有機系繊維、例えば、ポリオレフィン系繊維（例えば、ポリプロピレン繊維）またはＰＶＡ系繊維であってもよい。
Among these, 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. Can be advantageously used.
The alkali resistant fiber may be an organic fiber, for example, a polyolefin fiber (for example, polypropylene fiber) or a PVA fiber.
セメントとの接着性が良好であるだけでなく、ホウ酸含有化合物との結合性に優れるため、特にＰＶＡ系繊維が耐アルカリ性繊維として好ましい。耐アルカリ性繊維としてＰＶＡ系繊維を用いる場合、乾式紡糸で作製したＰＶＡ繊維または有機溶媒を用いた湿式紡糸で作製したＰＶＡ繊維を用いることが好ましい。 PVA fibers are particularly preferable as alkali-resistant fibers because they have not only good adhesion to cement but also excellent bonding properties with boric acid-containing compounds. When using 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.
（ホウ酸含有化合物）
本発明においては、耐アルカリ性繊維の繊維表面にホウ酸含有化合物が付着している。ホウ酸含有化合物は、ホウ酸であってもよい。あるいは、ホウ酸塩であってもよい。ホウ酸塩としては、例えば、ホウ酸ナトリウム、ホウ酸カリウム、ホウ酸アンモニウム等が挙げられる。これらのホウ酸含有化合物は、単独でまたは二種以上組み合わせて使用してもよい。例えば、ホウ酸および二種以上のホウ酸塩からなる群から選択される少なくとも一種（一種または二種以上）の化合物を用いてもよい。
(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.
ホウ酸含有化合物の量は、全繊維質量（実質的に耐アルカリ性繊維とホウ酸含有化合物からなる繊維においては、耐アルカリ性繊維とホウ酸含有化合物の合計質量）に対して、０．０１質量％以上、５質量％以下であることが必要である。ホウ酸含有化合物の量は、好ましくは３質量％以下であってもよく、より好ましくは２質量％以下であってもよく、さらに好ましくは１質量％未満であってもよい。なおホウ酸含有化合物の付着量は、乾燥状態の繊維において、上記の範囲となるように調整すればよい。 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.
なお、ホウ酸含有化合物の付着量は、例えばＩＣＰ法や、マンニトールを用いた滴定法により測定することができる。 In addition, the adhesion amount of the boric acid-containing compound can be measured by, for example, an ICP method or a titration method using mannitol.
（補強繊維の繊維径およびアスペクト比）
水硬性成形体用補強繊維の繊維径は、用途、目的に応じて適宜変更すれば良く、例えば１０〜１０００μｍ程度であってもよく、好ましくは１００〜９００μｍ程度、より好ましくは２００〜８００μｍ程度（例えば、２００〜３００μｍ程度）であってもよい。特に、本発明では、ホウ酸含有化合物を用いることにより、繊維径の太い補強繊維であっても、水硬化性成形体材料に対して、流動性と補強性の双方を両立させることができる。実質的には、耐アルカリ性繊維の繊維径が上記の数値範囲内であればよい。
(Fiber diameter and aspect ratio of reinforcing fiber)
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 μm, preferably about 100 to 900 μm, more preferably about 200 to 800 μm ( For example, it may be about 200 to 300 μm. In particular, in the present invention, by using a boric acid-containing compound, both fluidity and reinforcing property can be achieved with respect to the water-curable molded material even if the reinforcing fiber has a large fiber diameter. Essentially, the fiber diameter of the alkali-resistant fiber may be in the above numerical range.
本発明の水硬性成形体用補強繊維は通常短繊維で用いられ、ホウ酸含有化合物の付着により水硬性材料の流動性が抑圧されないため、繊維のアスペクト比（繊維長／繊維径の比）が小さい単繊維の状態で用いることができる。そのため、繊維のアスペクト比は、例えば３０〜５００程度であってもよく、好ましくは４５〜４５０程度であってもよい。例えば、アスペクト比は、約４５以上、約１００以下であってもよい。実質的には、耐アルカリ性繊維のアスペクト比が上記の範囲内であればよい。
繊維径は公知の方法によって測定できる。繊維径は、繊維の繊度と繊維材料の密度から計算した数値（繊維断面を真円と仮定して計算した直径）であってもよい。繊維の繊度は、例えば、ＪＩＳ Ｌ１０１５「化学繊維ステープル試験方法（８．５．１）」に準じて決定できる。アスペクト比は、繊維径と繊維長より計算できる。
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.
（補強繊維の製造方法）
補強繊維は、耐アルカリ性繊維を紡糸あるいは紡糸乾燥した後、ホウ酸含有化合物を含む溶液または分散液を繊維に対して付着させることにより行われる。その後、繊維表面から溶媒または分散媒を乾燥除去することにより、表面にホウ酸含有化合物が付着した耐アルカリ性繊維が得られる。例えば、ホウ酸含有化合物を含む溶液または分散液をローラーあるいはスプレーなどを用いて繊維に塗布してもよい。あるいは、ホウ酸含有化合物を含む溶液または分散液に繊維を浸漬して溶液または分散液を繊維表面に付着させてもよい。このホウ酸含有化合物の付着処理は、複数の繊維からなる繊維トウ（fiber tow）に対して行ってもよい。耐アルカリ性繊維は、紡糸後、ホウ酸含有化合物を付着させる前に、必要に応じ、延伸および／または切断してもよい。なお、炭素繊維の場合は、紡糸乾燥後、さらに焼成工程を経た繊維トウに対して、ホウ酸含有化合物を含む溶液または分散液が付着される。溶媒または分散媒としては、水などを用いてもよい。なおこれらの液体には、必要に応じて各種添加剤が含まれていてもよい。
(Manufacturing method of reinforcing fiber)
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. For example, a solution or dispersion containing a boric acid-containing compound may be applied to the fiber using a roller or a spray. Alternatively, 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. In the case of carbon fiber, after spinning and drying, 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.
なお、特開平１０−２６６０１６号公報に記載されているように、紡糸乾燥後の繊維トウに対してホウ酸含有化合物の溶液又は分散液を適用する場合、ホウ酸含有化合物は個々の繊維内部にはほとんど侵入しないと考えられている。 As described in JP-A-10-266016, when a solution or dispersion of a boric acid-containing compound is applied to a fiber tow after spinning and drying, the boric acid-containing compound is contained in each fiber. Are thought to hardly penetrate.
アスペクト比を調整するため、ホウ酸含有化合物を付着させた後、繊維を切断してもよい。この場合、ホウ酸含有化合物は側面に付着していればよく、端面（断面）には付着していなくてもよい。 In order to adjust the aspect ratio, the fiber may be cut after the boric acid-containing compound is attached. In this case, the boric acid-containing compound may be attached to the side surface, and may not be attached to the end surface (cross section).
このホウ酸含有化合物が付着した耐アルカリ性繊維は、必要に応じて、さらに乾燥させて用いることができる。乾燥させた場合、その水分量は、全繊維重量に対して、例えば０．１質量％未満であってもよい。 The alkali-resistant fiber to which the boric acid-containing compound is adhered can be further dried and used as necessary. When dried, the moisture content may be, for example, less than 0.1% by mass relative to the total fiber weight.
なお、実際の製造にあたっては、予備試験により、所定の繊維径を得られる紡糸、延伸等の条件、所定のホウ酸含有化合物付着量を得られる溶媒、分散媒の濃度などの製造条件を決定し、この条件に従って製造を行えばよい。なお、繊維のアスペクト比は、繊維径に対応して繊維を所定の長さに切断することにより、調整できる。 In actual production, 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系繊維）
上記本発明の補強繊維を構成する耐アルカリ性繊維としてＰＶＡ系繊維を用いる場合、下記の特性を有するＰＶＡ系繊維を用いることができる。
ＰＶＡ系繊維を構成するＰＶＡ系ポリマーの重合度は、目的に応じて適宜選択でき特に限定されるものではないが、得られる繊維の機械的特性等を考慮すると３０℃水溶液の粘度から求めた平均重合度が５００〜２００００程度（好ましくは８００〜１５０００程度、さらに好ましくは１０００〜１００００程度）のものであってもよい。このうちでも、ＰＶＡ系ポリマーの平均重合度は、強度の観点から１０００以上であることが好ましく、１２００以上であることがより好ましく、１５００以上であることがさらに好ましく、１７５０以上であることがなお好ましい。ＰＶＡ系ポリマーは、平均重合度１０００以上３０００未満の中重合度品であってもよいが、平均重合度３０００以上の高重合度品であってもよい。
(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). Among these, 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. preferable. 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.
また、ＰＶＡ系ポリマーのけん化度も、目的に応じて適宜選択でき特に限定されるものではないが、得られる繊維の力学物性の点から、例えば９５モル％以上、より好ましくは９８モル％以上であってもよい。けん化度は９９モル％以上であってもよく、９９．８モル％以上であってもよい。ＰＶＡ系ポリマーのけん化度が低すぎると、得られる繊維の機械的特性や工程通過性、製造コストなどの面で好ましくない場合が多い。 Further, 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.
本発明に用いられるＰＶＡ系繊維は、このようなＰＶＡ系ポリマーを溶剤に溶解し、湿式、乾湿式、乾式のいずれかの方法により紡糸し、乾熱延伸する事により得られる。なお、湿式紡糸とは、紡糸ノズルから直接固化浴に紡糸原液を吐出する方法のことであり、乾湿式紡糸とは、紡糸ノズルから一旦任意の距離の空気中あるいは不活性ガス中に紡糸原液を吐出し、その後に固化浴に導入する方法のことである。また、乾式紡糸とは、空気中あるいは不活性ガス中に紡糸原液を吐出する方法のことである。
ＰＶＡ系繊維は、紡糸後、必要に応じて延伸処理が行われてもよい。また、ＰＶＡ系繊維で一般的に行われているアセタール化処理などが行われてもよい。
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 into a solidification bath, and dry and wet spinning is a method in which a spinning stock solution is temporarily placed in 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.
ＰＶＡ系繊維の紡糸原液に用いられる溶剤としては、ＰＶＡを溶解することが可能な溶剤であれば特に限定されない。例えば水、ジメチルスルホキシド（ＤＭＳＯ）、ジメチルホルムアミド、ジメチルアセトアミド、グリセリン、エチレングリコール、トリエチレングリコール等の多価アルコールなどの１種または２種以上を組み合わせて用いることができる。本発明では、湿式紡糸を行う場合、溶剤としては有機系の溶剤を用いることが好ましい。この中でも、供給性、環境負荷への影響の観点から、ＤＭＳＯが特に好ましい。紡糸原液中のポリマー濃度は、ＰＶＡ系ポリマーの組成や重合度、溶剤の種類によって異なるが、６〜６０質量％の範囲が一般的である。 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. 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. In the present invention, when performing wet spinning, it is preferable to use an organic solvent as the solvent. Among these, 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.
乾式紡糸でも、上記の溶剤を用いることができる。その場合、水を用いても、有機系の溶剤を用いてもよい。 The above solvent can also be used in dry spinning. In that case, water or an organic solvent may be used.
本発明の効果を損なわない範囲であれば、紡糸原液にはＰＶＡ系ポリマー以外にも、目的に応じて、界面活性剤、酸化防止剤、分解抑制剤、凍結防止剤、ｐＨ調整剤、隠蔽剤、着色剤、油剤などの添加剤などが含まれていてもよい。 As long as the effects of the present invention are not impaired, 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.
固化浴で用いられる溶媒は、紡糸原液で用いられる溶剤の種類に応じて適宜選択することができる。紡糸原液が水溶液の場合、固化浴としては、例えば、硫酸ナトリウム、硫酸アンモニウム、炭酸ナトリウム等のＰＶＡ系ポリマーに対して固化能を有する無機塩類や水酸化ナトリウムの水溶液を用いることができる。紡糸原液が有機溶剤溶液の場合、固化浴としては、例えばメタノール、エタノール、プロパノール、ブタノールなどのアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類等のＰＶＡ系ポリマーに対して固化能を有する有機溶媒を用いることができる。 The solvent used in the solidification bath can be appropriately selected according to the type of solvent used in the spinning dope. When the spinning dope is an aqueous solution, as the solidification bath, for example, 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. When 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.
本発明においては、乾式紡糸で得られる繊維、または有機溶剤を溶媒とする紡糸原液から湿式紡糸で得られる繊維が、繊維強度の点から好ましい。 In the present invention, 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.
固化された原糸から紡糸原液の溶媒を抽出除去するために、抽出浴を通過させてもよく、抽出時に同時に原糸を湿延伸してもよい。また、湿延伸後、繊維を乾燥させ、必要に応じて、さらに乾熱延伸を行ってもよい。延伸を行う場合、総延伸倍率（湿延伸と乾燥後の延伸倍率の積）として、例えば、５〜２５倍、好ましくは８〜２０倍程度の延伸を行ってもよい。
このようにして製造されたＰＶＡ系繊維の表面にホウ酸含有化合物を付着させることにより、本発明に係る水硬成形体補強繊維として用いることができる。
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 the wet stretching and the stretching ratio after drying) may be, for example, 5 to 25 times, preferably about 8 to 20 times.
By attaching a boric acid-containing compound to the surface of the PVA-based fiber thus produced, it can be used as a hydraulic molded body reinforcing fiber according to the present invention.
［水硬性材料］
本発明の第２の実施形態にかかる、水硬性材料は、水硬性無機物質と、上記の第1実施形態で説明された補強繊維とを含む水硬性材料である。このような材料は、繊維で補強された水硬性成形体の形成に用いることができる。
この水硬性材料としては、セメントを含む組成物や石膏を含む石膏組成物などが挙げられる。
セメントを含む水硬性材料として、セメントペースト、モルタル、コンクリートなどを挙げることができる。セメントペーストは、セメントと水を含む組成物であり、モルタルは、セメントと水と細骨材を含む組成物であり、コンクリート（フレッシュコンクリート）は、通常、セメントと水と細骨材と粗骨材を含む組成物である。これらの組成物には、必要に応じ、各種の混和材料（混和材・混和剤）が含まれ、本発明においては、補強繊維が含まれる。
また水添加前の固形分の混合物からなるセメント組成物、モルタル用組成物、コンクリート用組成物も本発明に係る水硬性材料として挙げることができる。これらの組成物に水を添加して練り混ぜることにより、セメントペースト、モルタル、コンクリートなど、水を含有する状態の水硬性材料を形成することができる。
[Hydraulic material]
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.
Examples of the hydraulic material include a composition containing cement and a gypsum composition containing gypsum.
Examples of 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, and concrete (fresh concrete) is usually cement, water, fine aggregate and coarse bone. It is a composition containing a material. These compositions contain various admixtures (admixtures / admixtures) as necessary, and in the present invention, reinforcing fibers are included.
Further, 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. By adding water to these compositions and kneading, a hydraulic material containing water such as cement paste, mortar, concrete, or the like can be formed.
水硬性材料に含まれる水硬性無機物質としては、セメント、石膏などが挙げられる。セメント（水硬性セメント）としては、例えば、普通ポルトランドセメント、早強ポルトランドセメント、低熱セメント、中庸熱ポルトランドセメントなどのポルトランドセメント、アルミナセメント、高炉セメント、シリカセメント、フライアッシュセメント、エコセメントなどが挙げられる。また、石膏としては、２水石膏、α型又はβ型半水石膏、無水石膏等が挙げられる。これらの水硬性無機物質は、単独でまたは二種以上組み合わせて使用してもよい。これらの水硬性無機物質は、通常粉末（微粒子）の状態で用いられ、添加された水と反応して凝結し、水硬性材料を硬化させる。 Examples of the hydraulic inorganic substance contained in the hydraulic material include cement and gypsum. Examples of 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, α-type or β-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.
水硬性材料には、必要に応じ、各種の骨材が含まれていてもよい。例えば、そのような骨材として、細骨材、粗骨材などが挙げられる。これらの骨材は、単独でまたは二種以上組み合わせて使用してもよい。 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.
細骨材としては、例えば、粒径が５ｍｍ以下である細かい粒子が挙げられる。このような粒径を満たす限り、特に限定されないが、例えば、細骨材として用いられる材料としては、川砂、山砂、海砂、砕砂、珪砂、鉱滓、ガラス砂、鉄砂、灰砂、炭酸カルシウム、人工砂等の砂類が挙げられる。 Examples of the fine aggregate 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. For example, 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 Examples include sands such as calcium and artificial sand.
粗骨材は、粒径５ｍｍ以上の粒子が重量％で８５％以上含まれる骨材である。粗骨材は、粒径５ｍｍ超の粒子からなるものであってもよい。例えば、各種砂利類、人工骨材（高炉スラグなど）、再生骨材（建築廃材の再生骨材など）などを用いることができる。 Coarse aggregate is an aggregate containing 85% or more by weight of particles having a particle size of 5 mm or more. The coarse aggregate may be composed of particles having a particle size of more than 5 mm. For example, various gravels, artificial aggregates (such as blast furnace slag), recycled aggregates (such as recycled aggregates of building waste), and the like can be used.
上記の骨材（細骨材及び／または粗骨材）には、軽量骨材が含まれていてもよい。軽量骨材としては、火山砂利、膨張スラグ、炭殻などの天然軽量骨材、発泡真珠岩、発泡パーライト、発泡黒よう石、バーミキュライト、シラスバルーン等の人工軽量骨材が挙げられる。 The aggregate (fine aggregate and / or coarse aggregate) may include a lightweight aggregate. Examples of 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.
水硬性材料には、適宜、必要に応じて、各種の混和材料を混入してもよい。ここで、混和材料は、水硬性無機物質と水と骨材以外に、水硬性材料に混入される物質である。混和材料としては、例えば、シリカフューム、フライアッシュ、高炉スラグ微粉末、石灰石粉末、石英粉末などの混和材、またＡＥ剤、流動化剤、減水剤、高性能減水剤、ＡＥ減水剤、高性能ＡＥ減水剤、増粘剤、保水剤、撥水剤、膨張剤、硬化促進剤、凝結遅延剤などを挙げることができる。これらの混和材料は、単独でまたは二種以上組み合わせて使用してもよい。 Various kinds of admixtures may be mixed into the hydraulic material as necessary. Here, the admixture is a substance mixed in the hydraulic material in addition to the hydraulic inorganic substance, water, and aggregate. Examples of 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. Examples thereof 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. These admixtures may be used alone or in combination of two or more.
補強繊維、水硬性無機物質、骨材、混和材料等の配合量及び水の添加量は、所望とする成形体に応じて、適宜調整できる。適宜公知の配合量を用いてもよい。ただし、本発明で用いられる水硬性成形体用補強繊維は、繊維自体の働きにより高い流動性を水硬性材料に対して与えることができるため、流動化剤などの使用量を低減し、水硬性成形体の強度を向上することができる。 The amount of the reinforcing fiber, the hydraulic inorganic substance, the aggregate, the admixture, and the like 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. However, since 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.
本発明においては、水硬性材料に補強繊維が混和される。この補強繊維は、上記の第１の実施形態１の記載で説明したものを用いることができる。水硬性材料の形態によって適宜選択することが可能であるが、例えば、補強繊維の質量Ｆとセメントの質量Ｃの比は、Ｆ／Ｃ＝１／３００〜１００／１０００程度であってもよく、好ましくは１０／５００〜７０／８００程度であってもよく、より好ましくは３０／５００〜５０／７００程度であってもよい。 In the present invention, reinforcing fibers are mixed in the hydraulic material. As the reinforcing fibers, those described in the description of the first embodiment can be used. Although it can be appropriately selected depending on the form of the hydraulic material, for example, the ratio of the mass F of the reinforcing fiber and the mass C of the cement may be about F / C = 1/300 to 100/1000, Preferably, it may be about 10/500 to 70/800, more preferably about 30/500 to 50/700.
本発明の水硬性材料では、例えば、水の質量をＷ、セメントの質量をＣとしたときの、水セメント比（Ｗ／Ｃ）が１５〜６０％程度であってもよく、好ましくは１８〜４０％、より好ましくは２０〜３０％であってもよい。
また、その流動性を表す指標として、水とセメントの合計量における水セメント比が２０〜３０％の場合、例えばそのフロー値が１７５〜３００ｍｍ程度であってもよく、より好ましくは１８０〜２５０ｍｍ程度であってもよい。このフロー値は、JIS R 5201 セメントの物理試験方法 記載のフロー試験法により求めることができる。
In the hydraulic material of the present invention, for example, 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%.
Further, as an index representing the fluidity, when the water cement ratio in the total amount of water and cement is 20 to 30%, for example, 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.
前記水硬性材料を硬化することにより、成形体を得ることができる。このような水硬性成形体は、水硬性材料を用いて所望の形態に成形した後、硬化させたものであり、各種建設資材、土木資材として利用することができる。例えば、セメント含有組成物を材料とする建設資材（例えば、建築構造物の基礎、屋根材、外壁材、間仕切り、天井材など）、土木資材（例えば、橋梁、高速道路、トンネル、法面補強材、テトラポットなど）として有用に用いることができる。水硬性材料の成形工程、成形した水硬性材料の硬化工程は、公知の方法に従って行うことができる。 A molded body can be obtained by curing the hydraulic material. Such 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. For example, construction materials (for example, foundations of building structures, roofing materials, exterior wall materials, partitions, ceiling materials, etc.) and 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.
以上のとおり、本発明の好適な実施形態を説明したが、本発明の趣旨を逸脱しない範囲で、種々の追加、変更または削除が可能であり、そのようなものも本発明の範囲内に含まれる。 As described above, the preferred embodiments of the present invention have been described. However, various additions, modifications, or deletions are possible without departing from the spirit of the present invention, and such modifications are also included in the scope of the present invention. It is.
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明は、これらの実施例に限定されるものではない。
以下に実施例で求めた数値の評価方法について説明する。これらの方法は、上述の実施形態における数値評価に適用してもよい。
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
The evaluation method of the numerical value calculated | required by the Example below is demonstrated. These methods may be applied to the numerical evaluation in the above-described embodiment.
［水硬性材料のフロー値］
JIS R 5201 セメントの物理試験方法 記載のフロー試験により、水硬性材料のフロー値を求めた。JIS R 5201では、フローコーンを取り去った後で１５秒間に１５回の落下運動を与えることとしており、これに従って求めた水硬性材料のフロー値を１５打フロー値とした。
また別に、落下運動を与えない場合についてもフロー値を測定し、これを０打フロー値とした。この場合、JIS R 5201 セメントの物理試験方法 記載の方法に準じて、水硬性材料を規格サイズのフローコーンに充填した。次いでフローコーンを取り去った後１２０秒後の時点で、広がった水硬性材料の径を最大と認める方向と、これに直角な方向とで測定し、その平均値をmmを単位とする整数で示した。
[Flow value of hydraulic material]
JIS R 5201 cement physical test method The flow value of the hydraulic material was determined by the flow test described. In JIS R 5201, after removing the flow cone, 15 drop motions are given in 15 seconds, and the flow value of the hydraulic material determined in accordance with this is set to 15 stroke flow values.
Separately, the flow value was also measured when no drop motion was given, and this was taken as the zero stroke flow value. In this case, a hydraulic material was filled into a standard size flow cone according to the method described in the physical test method of JIS R 5201 cement. Next, at the time 120 seconds after the flow cone was removed, measurement was performed in the direction in which the diameter of the expanded hydraulic material was recognized as the maximum, and the direction perpendicular thereto, and the average value was expressed as an integer in mm. It was.
［水硬性成形体の圧縮強度測定試験］
JIS A 1108 コンクリートの圧縮強度試験方法による。ミキサーで混練されたモルタルを直径50mm、高さ100mmの型枠に流し込んだ後、20℃の室内で48時間封緘養生し脱型したものを湿布で包み温度90℃・湿度98％の恒温恒湿槽で48時間湿熱養生して強度試験に供した。圧縮強度試験は最大容量2000ｋNの万能試験機にて行った。
[Compressive strength measurement test of hydraulic molded body]
According to JIS A 1108 concrete compressive strength test method. After pouring mortar kneaded with a mixer into a mold with a diameter of 50mm and a height of 100mm, sealed and cured in a room at 20 ° C for 48 hours, wrapped in a compress, and kept at a temperature of 90 ° C and humidity of 98% It was subjected to wet heat curing in a tank for 48 hours and subjected to a strength test. The compressive strength test was conducted with a universal testing machine having a maximum capacity of 2000 kN.
［水硬性成形体の曲げ強度測定試験］
JIS A 1106 コンクリートの曲げ強度試験方法による。ミキサーで混練されたモルタルを、断面が40mm×40mmで長さが160mmの角柱形状の型枠に流し込んだ後、20℃の室内で48時間封緘養生し脱型したものを湿布で包み温度90℃・湿度98％の恒温恒湿槽で48時間湿熱養生して強度試験に供した。曲げ強度試験は最大容量2000ｋNの万能試験機にて行った。尚、曲げ強度は、成形体の比例限界強度（LOP: Limit of Proportionality）でなく、最大耐力（MOR: Modulus of Rupture)として測定した。
[Bending strength measurement test of hydraulic compacts]
According to JIS A 1106 concrete bending strength test method. After pouring the mortar kneaded with a mixer into a prismatic formwork with a cross section of 40 mm x 40 mm and a length of 160 mm, sealed and cured in a 20 ° C room for 48 hours, wrapped in a compress and heated at 90 ° C・ Heat and heat curing was performed for 48 hours in a constant temperature and humidity chamber with a humidity of 98% and subjected to a strength test. The bending strength test was conducted with a universal testing machine having a maximum capacity of 2000 kN. The bending strength was measured not as a proportional limit strength (LOP) of the molded body but as a maximum proof strength (MOR: Modulus of Rupture).
［水硬性成形体の嵩密度］
水硬性成形体の嵩密度は、上記の曲げ強度測定試験用に作製した、断面が40mm×40mmで長さが160mmの角柱形状の試験片の重量を測定し、以下の式により算出した。
嵩密度（g/cm3）＝試験片重量（g）÷試験片体積（cm3）
ここで、試験片の体積は256cm3として計算した。
[Bulk density of hydraulic compact]
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 )
Here, the volume of the test piece was calculated as 256 cm 3 .
［ホウ酸含有化合物の付着量］
ホウ酸含有化合物の付着量は、滴定によるマンニトール法により測定した。実施例では、繊維表面のホウ酸を水に溶解させ、ホウ素と反応し易いマンニトール（マンニット）を添加し、ＮａＯＨの滴定によりホウ酸含有化合物の量を求め、繊維表面に付着しているホウ酸含有化合物の量を定量した。
[Amount of adhered boric acid-containing compound]
The adhesion amount of the boric acid-containing compound was measured by a mannitol method by titration. In the examples, 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.
［繊維径およびアスペクト比の測定方法］
ＪＩＳ Ｌ１０１５「化学繊維ステープル試験方法（８．５．１）」に準じて評価した。まずＪＩＳ記載の方法に従って、繊維の繊度を求め、材料の密度と繊維の繊度から繊維径を計算した。アスペクト比は、繊維径と繊維長より計算した。
[Measurement method of fiber diameter and aspect ratio]
Evaluation was made according to JIS L1015 “Testing method for chemical fiber staples (8.5.1)”. First, the fineness of the fiber was determined according to the method described in JIS, and the fiber diameter was calculated from the density of the material and the fineness of the fiber. The aspect ratio was calculated from the fiber diameter and fiber length.
［実施例１］
ポリマー重合度１７５０、ケン化度９９．９モル％のＰＶＡを用い、ＰＶＡ濃度が２１質量％となるようにＤＭＳＯに溶解し紡糸原液とし、メタノールとＤＭＳＯの混合溶媒を固化浴に用いて湿式紡糸にて紡糸した。さらにメタノールでＤＭＳＯを抽出しながら、湿延伸、乾燥後、乾熱延伸（延伸温度２３０℃、総延伸倍率１３倍）を実施した。延伸したＰＶＡ繊維に対して、ホウ酸水溶液（ホウ酸濃度：３ｇ／Ｌ）をローラータッチにより表面に付着させた後、乾燥させることで、ＰＶＡ繊維に対してホウ酸を付着させた。その後切断して、繊維径２５０μｍ、アスペクト比６０のホウ酸付着ＰＶＡ繊維を得た。繊維のホウ酸付着量は、関東化学（株）製マンニットを用い、マンニトール法による滴定を元に算出した。
[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. Thereafter, cutting was performed to obtain a boric acid-attached PVA fiber having a fiber diameter of 250 μm 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.
最大容量20Lのホバートミキサーに、普通セメント（太平洋セメント（株）製）６００重量部、シリカフューム（EFACO社製）４００重量部、細骨材（６．５号硅砂：最大径約１mm）９００重量部、水１５０重量部、ポリカルボン酸系高性能AE減水剤（竹本油脂（株）製「SSP-104」）２５重量部を約２L容量になる容積で１２分間混練し、出来上がったプレーンモルタルに、繊維を３５重量部添加し２分間の追加混練して、水硬性材料として繊維補強モルタルを作製した。
次いで、このモルタルを直径50mm、高さ100mmの型枠に流し込んだ後、20℃の室内で48時間封緘養生し、脱型したものを湿布で包み温度90℃・湿度98％の恒温恒湿槽で48時間湿熱養生し、水硬性成形体を作製し、圧縮強度を測定した。
別に、上記のモルタルを断面が40mm×40mmで長さが160mmの角柱形状の型枠に流し込んだ後、20℃の室内で48時間封緘養生し脱型したものを湿布で包み、温度90℃・湿度98％の恒温恒湿槽で48時間湿熱養生して成形体試験片を作製し、重量と体積から成形体の嵩密度を計算した後、曲げ強度試験に供した。
また別に、上記のモルタルについて、JIS R 5201 セメントの物理試験方法 記載の方法を用いてフロー試験を行い、１５打フロー値を求めた。別にフローコーン除去後、落下運動を与えない場合について、上記の方法に従い、０打フロー値を求めた。
繊維のホウ酸付着量、モルタルのフロー値、成形体の圧縮強度、成形体の曲げ強度（最大耐力）、成形体の嵩密度を表１に示す。
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.
Next, after pouring this mortar into a mold with a diameter of 50 mm and a height of 100 mm, it was sealed and cured in a room at 20 ° C for 48 hours, and the demolded material was wrapped in a compress and kept at a temperature of 90 ° C and humidity of 98%. Was subjected to wet heat curing for 48 hours to produce a hydraulic molded body, and the compressive strength was measured.
Separately, the above 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.
Separately, 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. Separately, after removing the flow cone, 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.
［実施例２〜５］
耐アルカリ性繊維に対するホウ酸の付着量を表１の組成に変更する以外は実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[Examples 2 to 5]
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.
［実施例６］
繊維径を３００μｍ、アスペクト比を５０とし、ホウ酸の付着量を０．３質量％とした以外は実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[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 μm, 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.
［実施例７］
繊維のアスペクト比を４８とし、ホウ酸の付着量を０．３質量％とした以外は実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[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.
［実施例８］
ポリプロピレン（ＰＰ）繊維を準備し、ホウ酸水溶液をローラータッチで塗布させたのち、切断して繊維径２５０μｍ、アスペクト比６０のホウ酸付着ＰＰ繊維を得た。マンニトール法で測定されたホウ酸付着量は０．３質量％であった。この繊維を用いる以外は実施例１と同様にして水硬性材料（モルタル）を作製し、水硬性材料のフロー値よび水硬性成形体の圧縮強度、最大耐力と嵩密度を求めた。その結果を表１に示す。
[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 μm 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.
［比較例１］
ホウ酸を付着することなく、ＰＶＡ系繊維を得る以外は、実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[Comparative 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.
［比較例２］
耐アルカリ性繊維に対するホウ酸の付着量を表１の組成に変更する以外は実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[Comparative 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.
［比較例３］
ホウ酸の付着量を６質量％とする以外は、実施例１と同様にして、ＰＶＡ系繊維、水硬性材料および水硬性成形体を作製した。
得られた水硬性材料のフロー値および水硬性成形体の圧縮強度、最大耐力と嵩密度を表１に示す。
[Comparative 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.
［比較例４］
実施例１における繊維添加前のプレーンモルタルと同様にして、補強繊維を含まないモルタルを作製した。このモルタルを用い、実施例１と同様に、フロー値、嵩密度、成形体圧縮強度の測定、および曲げ強度試験を行った。その結果を表１に示す。曲げ強度試験では、比例限界強度（ＬＯＰ）に達した後、成形体が破断し、成形体の塑性変形領域で測定される最大耐力は検出できなかった。
[Comparative 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.
表１に示すように、実施例１〜７は、いずれも水硬性材料の流動性を示す０打フロー値、１５打フロー値が高い状態であり、しかも得られた成形体の圧縮強度が高い値を示している。実施例１〜７が示す高い嵩密度も、水硬性材料の流動性がよく、結果として緻密な成形体が形成されたことを示している。実施例８が示すように、ＰＶＡ以外の補強繊維に本発明で規定する範囲内の量でホウ酸を付着させた場合にも、水硬性材料の流動性を高めるとともに、成形体の圧縮強度を高い値に維持する効果が確認された。 As shown in Table 1, each of Examples 1 to 7 is in a state where the 0-stroke flow value and the 15-stroke flow value indicating the fluidity of the hydraulic material are high, and the compression strength of the obtained molded body is high. 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. As 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.
一方、ホウ酸が繊維に対して付着されていない比較例１では、０打フロー値、１５打フロー値に示されるように水硬性材料の流動性が低下するため、作業性が劣る。また成形体の嵩密度も実施例１〜７に比べて低く、モルタルの流動性の低下に起因して空隙の容積率が増加していることを示している。また、あまりに微量のホウ酸であっても、比較例２に示すように、ホウ酸が付着する効果は見られず、比較例１と同程度の結果を示す。
さらに、比較例３で示すように、ホウ酸の付着量が多すぎる場合、繊維表面のセメントとの濡れ性が悪くなるためか、水硬性材料の流動性および成形体の圧縮強度が悪化しており、最大耐力で示される曲げ強度も実施例に比べ不十分であった。
On the other hand, in 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. Moreover, the bulk density of a molded object is also low compared with Examples 1-7, and it has shown that the volume ratio of a space | gap has increased due to the fall of the fluidity | liquidity of a 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.
Furthermore, as shown in Comparative Example 3, when the adhesion amount of boric acid is too large, the wettability with the cement on the fiber surface is degraded, or the fluidity of the hydraulic material and the compression strength of the molded body are degraded. Therefore, the bending strength indicated by the maximum proof stress was also insufficient as compared with the examples.
モルタルに補強繊維を添加しない比較例４においては、フロー値、嵩密度が示す流動性と成形体圧縮強度に関しては良好な結果が得られている。しかし、曲げ強度試験においては、比例限界強度に達した時点で成形体が破断し、最大耐力は測定できなかった。これに対し、本発明に係る実施例１〜８では高い最大耐力が測定され、比較例４の成形体に比べ、顕著な曲げ強度の向上が認められた。 In Comparative Example 4 in which the reinforcing fiber is not added to the mortar, good results are obtained with respect to the flowability and the compact compression strength indicated by the flow value and the bulk density. However, in the bending strength test, when the proportional limit strength was reached, the molded body broke and the maximum yield strength could not be measured. In contrast, in Examples 1 to 8 according to the present invention, a high maximum proof stress was measured, and a marked improvement in bending strength was recognized as compared with the molded body of Comparative Example 4.
本発明によれば、補強繊維を含む水硬性材料に、硬化後の圧縮強度を損なうことなく、高い流動性を付与することができる。従って、高い圧縮強度を維持しつつ、繊維補強による曲げ強度向上等の効果も有する水硬性成形体を高い成形性で形成することができる。
本発明の水硬性成形体用補強繊維を配合したセメントペースト、モルタル、コンクリート等の水硬性材料の用途は特に限定されるものではなく、各種建設資材、土木資材として利用することができる。
ADVANTAGE OF THE INVENTION According to this invention, high fluidity | liquidity can be provided to the hydraulic material containing a reinforcing fiber, without impairing the compressive strength after hardening. Accordingly, it is possible to form a hydraulic molded body having high moldability while maintaining high compressive strength and having effects such as improvement of bending strength by fiber reinforcement.
The use of hydraulic materials such as cement paste, mortar, concrete, etc., in which the reinforcing fibers for hydraulic molded bodies of the present invention are blended is not particularly limited, and can be used as various construction materials and civil engineering materials.
Claims (14)
前記繊維表面に付着したホウ酸含有化合物とを有し、
前記ホウ酸含有化合物を０．０１〜５質量％含む水硬性成形体用補強繊維。 Alkali resistant fiber that is 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 ;
Boric acid-containing compound attached to the fiber surface,
A reinforcing fiber for a hydraulic molded body containing 0.01 to 5% by mass of the boric acid-containing compound.
請求項１〜７のいずれか一項に記載の水硬性成形体用補強繊維とを含む水硬性材料。 Hydraulic inorganic substances,
Hydraulic material comprising a hydraulic molded body reinforcing fiber according to any one of claims 1-7.
耐アルカリ性繊維を紡糸または準備する工程と、
前記耐アルカリ性繊維の表面にホウ酸含有化合物の溶液または分散液を付着させる工程と
前記耐アルカリ性繊維の表面から前記溶液または分散液の溶媒または分散媒を乾燥除去する工程と
を含む、水硬性成形体用補強繊維の製造方法。 A method of manufacturing a hydraulic molded body reinforcing fiber according to any one of claims 1 to 7
Spinning or preparing alkali resistant fibers;
A hydraulic forming process comprising: attaching a solution or dispersion of a boric acid-containing compound to the surface of the alkali-resistant fiber; and drying and removing the solvent or dispersion medium of the solution or dispersion from the surface of the alkali-resistant fiber. A method for producing body reinforcing fibers.
前記耐アルカリ性繊維を紡糸する工程において、乾式紡糸または有機溶媒を用いた湿式紡糸により、ポリビニルアルコール系繊維を紡糸する、水硬性成形体用補強繊維の製造方法。 A method for producing a reinforcing fiber for a hydraulic molded body according to claim 12 ,
A method for producing a reinforcing fiber for a hydraulic molded article, wherein, in the step of spinning the alkali-resistant fiber, a polyvinyl alcohol fiber is spun by dry spinning or wet spinning using an organic solvent.
水硬性無機物質と、請求項１〜７のいずれか一項に記載の補強繊維と、水と、必要に応じ細骨材、粗骨材、混和材料から選択される少なくとも一種とを練り混ぜて、含水混合物からなる水硬性材料を形成する工程と、
前記含水硬性材料を成形して成形体を形成する工程と、
前記成形体を硬化する工程と
を含む、
水硬性成形体の形成方法。 A method for forming a hydraulic molded body, comprising:
A hydraulic inorganic substance, the reinforcing fiber according to any one of claims 1 to 7 , water, and at least one selected from fine aggregates, coarse aggregates, and admixtures as necessary are kneaded. Forming a hydraulic material comprising a water-containing mixture;
Forming the molded body by molding the hydrous hard material;
Curing the molded body,
A method for forming a hydraulic molded body.
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