JP2006232651A - Admixture for extrusion molding of cement and extrusion molded cement product - Google Patents
Admixture for extrusion molding of cement and extrusion molded cement product Download PDFInfo
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- 238000001125 extrusion Methods 0.000 title claims abstract description 92
- 239000004568 cement Substances 0.000 title claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 38
- 229920002678 cellulose Polymers 0.000 claims abstract description 36
- 239000001913 cellulose Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000002736 nonionic surfactant Substances 0.000 claims description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- -1 alcohol ethylene oxide adducts Chemical class 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229920013820 alkyl cellulose Polymers 0.000 claims description 4
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 241000047703 Nonion Species 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 25
- 238000011156 evaluation Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 239000002131 composite material Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 9
- 235000012438 extruded product Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000010425 asbestos Substances 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052895 riebeckite Inorganic materials 0.000 description 4
- 229910021487 silica fume Inorganic materials 0.000 description 4
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- 235000019362 perlite Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 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
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 238000007664 blowing Methods 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
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003979 granulating agent Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、セメント押出成形用混和剤及びそれを加えて押出成形を行ったセメント押出成形体に関するものである。The present invention relates to an admixture for cement extrusion and a cement extrusion molded body obtained by adding the admixture.
従来、セメント押出成形体は普通ポルトランドセメントを始めとする水硬性物質、珪砂等の骨材、必要に応じて用いられる補強用繊維、軽量骨材等の各種組成物に水を加え粘土様の高粘性物質を作成し押出成形機を用いて平板、中空体等の所望の形状に製造されてきた。セメント系押出成形体を得るための成形用無機繊維として石綿（アスベスト）が系内への保形性導入を目的にセメント組成物中に混合使用されてきたが、石綿自体に発癌性が認められ使用が制限されるに至り、石綿に替わる押出成形用増粘剤としてメチルセルロース等のアルキルセルロース、ヒドロキシエチルセルロースやヒドロキシプロピルセルロース等のヒドロキシアルキルセルロース、ヒドロキシエチルメチルセルロースやヒドロキシプロピルメチルセルロース等のヒドロキシアルキルアルキルセルロースなどのセルロース系バインダーが優れた可塑性と保水性により成形物に高い成形性が導入することができるため幅広くセメント系押出成形用混和剤として使用されている。Conventionally, cement-extruded bodies have been made by adding water to various compositions such as hydraulic materials such as ordinary Portland cement, aggregates such as silica sand, reinforcing fibers used as needed, lightweight aggregates, etc. A viscous material has been prepared and manufactured into a desired shape such as a flat plate or hollow body using an extruder. Asbestos (asbestos) has been used in cement compositions for the purpose of introducing shape retention into the system as an inorganic fiber for molding to obtain cement-based extrudates, but asbestos itself has been found to be carcinogenic. As its use is limited, as an extrusion thickener to replace asbestos, alkylcellulose such as methylcellulose, hydroxyalkylcellulose such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcellulose such as hydroxyethylmethylcellulose and hydroxypropylmethylcellulose, etc. These cellulose binders are widely used as admixtures for cement-based extrusion because they can introduce high moldability into molded products due to excellent plasticity and water retention.
しかしながらセルロース系バインダーは出発原料としてコットンリンターや天然パルプ等の天然由来のセルロース繊維を用い反応工程、洗浄工程、粉砕工程等の繁雑な生産工程を経て製造される半合成天然高分子であるため非常に高価であるという問題点が存在する。さらにセルロース系バインダー自身の高い粘着性のため得られた成形物の滑り性と離形性が劣り、表面の平滑性が得られにくいとの欠点や押出速度の低下等による作業工程上の問題点、製造時の押出圧の上昇等による製造設備への負担増加などが認められてきた。However, cellulose-based binders are semi-synthetic natural polymers that are produced through complex production processes such as reaction, washing, and pulverization processes using cellulose fibers of natural origin such as cotton linter and natural pulp as starting materials. However, there is a problem that it is expensive. Furthermore, due to the high adhesiveness of the cellulosic binder itself, the slipping and releasability of the molded product is inferior, and it is difficult to obtain surface smoothness and problems in the work process due to reduced extrusion speed, etc. It has been recognized that the burden on manufacturing equipment is increased due to an increase in extrusion pressure during manufacturing.
これらの問題点を回避するためセルロース系バインダーの一部を比較的安価な化学合成品である減水剤に置き換えられて使用することが試みてこられてきた。例えば、特許文献１にはセルロース系バインダーとナフタレンスルホン酸ホルマリン縮合物系減水剤及び／又はメラミンスルホン酸ホルマリン縮合物系減水剤を併用して押出成形用助剤として系内に添加したセメント押出組成物が開示され、特許文献２にはポリカルボン酸系減水剤およびポリエーテル型非イオン性消泡剤を併用して用いられる押出成形助剤が開示されている。
しかしながら、特許文献１に記載のセルロース系バインダーとナフタレンスルホン酸ホルマリン縮合物系減水剤及び／又はメラミンスルホン酸ホルマリン縮合物系減水剤との併用系では減水剤のセメント粒子、骨材等への分散効果により押出成形時の流動性には大きな効果が認められ減水剤を用いない系と比較し製造時の押出速度の向上や生産時の押出圧の低下が確認されるものの、同時に減水剤の分散効果に起因する気泡連衡性等により成形品への保形性効果に関しては若干の効果は確認されるものの大きな効果は認められなかった。また、成形品における寸法変化等の大きな問題点も併せて確認された。
特許文献２に記載のセルロース系バインダー、ポリカルボン酸系減水剤、エーテル型非イオン性消泡剤の併用系では消泡剤の系内への気泡連衡性調整効果によりセルロース系バインダー、減水剤併用系において問題となった押出成形品の寸法変化等の保形性に関して著しい改善がみられた。しかしながら、通常セルロース系バインダーは粉末として減水剤は固形分１０−６０重量％程度の水溶液状態で市販されているため、セルロース系バインダー使用系よりセルロース系バインダーと減水剤併用系の検討を行う場合、通常粉体用原料ホッパーよりセルロース系バインダーを押出組成物系内に投入を行うがセルロース系バインダーと減水剤の併用系ではセルロース系バインダー用原料ホッパーなどの既存の押出製造設備では水溶液である減水剤の添加ができず新たに減水剤を用いるための受け入れタンク、計量装置、移送装置等の減水剤投入用の大規模な専用設備が必要となる。また、セルロース系バインダーと減水剤を併用使用する場合個別に計量後２成分を系内に投入するため安定に均一な押出組成物を得ることが難しい。さらに減水剤が水溶液であることに起因する在庫用の大規模倉庫の確保や製品納入時の運送費等のコスト面、減水剤自身に関する経時変化等による成分変質などの貯蔵安定性に関する大きな問題点が残り満足ができるものではなかった。However, in the combined use of the cellulose binder and the naphthalenesulfonic acid formalin condensate water reducing agent and / or the melamine sulfonic acid formalin condensate water reducing agent described in Patent Document 1, the water reducing agent is dispersed in cement particles, aggregates, and the like. Although the effect on fluidity at the time of extrusion molding is greatly confirmed due to the effect, an improvement in the extrusion speed during production and a decrease in the extrusion pressure during production are confirmed compared to a system that does not use a water reducing agent, but at the same time dispersion of the water reducing agent Although a slight effect was confirmed with respect to the shape retention effect on the molded product due to the bubble affinity due to the effect, a great effect was not recognized. In addition, major problems such as dimensional changes in the molded product were also confirmed.
In the combined use of the cellulose-based binder, polycarboxylic acid-based water reducing agent, and ether type nonionic antifoaming agent described in Patent Document 2, the cellulose-based binder and water reducing agent are used together due to the effect of adjusting the foam cohesion into the system. Significant improvements were observed with respect to shape retention, such as dimensional changes of extruded products, which became a problem in the system. However, since the cellulose binder is usually marketed in the form of an aqueous solution having a solid content of about 10 to 60% by weight as a powder, when examining a cellulose binder and a water reducing agent combined system rather than a cellulose binder using system, Cellulose binder is usually charged into the extrusion composition system from a raw material hopper for powders. In the combined use system of cellulose binder and water reducing agent, a water reducing agent that is an aqueous solution in existing extrusion manufacturing equipment such as a raw material hopper for cellulose binder. Therefore, a large-scale dedicated facility for introducing the water reducing agent such as a receiving tank, a measuring device and a transfer device for newly using the water reducing agent is required. In addition, when a cellulose binder and a water reducing agent are used in combination, it is difficult to obtain a stable and uniform extrusion composition because the two components are individually charged after weighing. In addition, large problems related to storage stability, such as securing large-scale warehouses for inventory due to the fact that the water reducing agent is an aqueous solution, transportation costs, etc. when delivering the product, and component alteration due to aging of the water reducing agent itself, etc. However, the rest was not satisfactory.
本発明は、上記のような従来技術の問題点を解決しセメント押出成形用混和剤として安価で押出成形時における流動性、押出成形物の保形性に優れる新規な粉体状のセメント押出成形用混和剤を提供することを目的とする。The present invention solves the problems of the prior art as described above and is a novel powder-like cement extrusion molding that is inexpensive as an admixture for cement extrusion and is excellent in fluidity during extrusion and shape retention of the extrusion. It is intended to provide an admixture for use.
本発明者らは、上記のような従来技術の問題点を解決するため鋭意検討した結果、あらかじめ減水剤及び／又はノニオン系界面活性剤、消泡剤を必要に応じてシリカ粉末に吸着させ粉粒状としセルロース系バインダーに混合した組成物を含む粉体状の押出成形用混和剤が安価で押出成形時における流動性や押出成形物の保形性に優れる新規なセメント押出成形用混和剤であることを見出し、本発明に至ったものである。As a result of intensive studies to solve the problems of the prior art as described above, the present inventors previously adsorbed a water reducing agent and / or a nonionic surfactant and an antifoaming agent on silica powder as necessary. A powdery extrusion molding admixture containing a composition mixed with a cellulose binder in the form of a granule is a new cement extrusion molding admixture that is inexpensive and has excellent fluidity during extrusion and shape retention of the extrusion. This has been found and the present invention has been achieved.
即ち本発明のセメント押出成形用混和剤は、セルロース系バインダー（Ａ）、減水剤（Ｂ−１）及び／又はノニオン系界面活性剤（Ｂ−２）、消泡剤（Ｃ）およびシリカ粉末（Ｄ）を含むことを特徴とする。
また本発明のセメント押出成形物は、セルロース系バインダー（Ａ）、粉末状消泡剤（Ｃ−１）および水を含有するセメント系組成物に、減水剤（Ｂ−１）及び／又はノニオン系界面活性剤（Ｂ−２）をシリカ粉末（Ｄ）に吸収させた粒粉状の混合物を添加し、押出成形したもの、或いはセルロース系バインダー（Ａ）と水を含有するセメント系組成物に、減水剤（Ｂ−１）及び／又はノニオン系界面活性剤（Ｂ−２）、液状消泡剤（Ｃ−２）をシリカ粉末（Ｄ）に吸収させた粒粉状の混合物を添加し、押出成形したものである。That is, the admixture for cement extrusion molding of the present invention comprises a cellulose binder (A), a water reducing agent (B-1) and / or a nonionic surfactant (B-2), an antifoaming agent (C) and silica powder ( D).
Moreover, the cement extrusion molding of this invention is a water-reducing agent (B-1) and / or a nonionic type | mold to the cement-type composition containing a cellulose-type binder (A), a powdery antifoamer (C-1), and water. To a cement-based composition containing a mixture of a powder form in which a surfactant (B-2) is absorbed in a silica powder (D) and extruded, or a cellulose-based binder (A) and water, Add water-reducing agent (B-1) and / or nonionic surfactant (B-2) and liquid antifoaming agent (C-2) to the silica powder (D), and add a granulated mixture Molded.
以下、本発明を詳しく説明する。本発明における押出成形用混和剤に用いるセルロース系バインダーとしてはアルキルセルロース、ヒドロキシアルキルセルロース、ヒドロキシアルキルアルキルセルロースなどのセルロース系バインダーが優れた可塑性と保水性により高い成形性を成形物に得ることができることから好ましく、具体的には一般的に市販されているメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロースやヒドロキシプロピルメチルセルロースが適する。セルロース系バインダーの粘度としては２０℃、１％水溶液をＢ型粘度計で測定したところ１００〜４００００ｍＰａ・ｓを示すものが適性を示すが、中でも８０００−４００００ｍＰａ・ｓの高い粘性を示すセルロース系バインダーが優れた可塑性と保水性により高い保形性を成形物系内に導入することができるため使用添加量を低減できるという点より比較的水溶液粘度が高い値を示すセルロース系バインダーが最も好ましい。優れた流動性、保形性を示す押出成形物を得るためのセルロース系バインダーの添加量としては水硬性物質、骨材等の合計量に対して０．１−１０．０重量％程度が一般的に使用されているが、コスト等の面を考慮に入れると添加量としては０．２−３．０重量％程度が望ましい。セルロース系バインダーの添加量が少なすぎる場合は十分な流動性、保形性を系内に導入できないことから優れた押出成形物を得ることができず、セルロース系バインダーの添加量が多すぎる場合は不必要にコスト高となるためである。The present invention will be described in detail below. Cellulose binders used for the extrusion molding admixture in the present invention include cellulose binders such as alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkylalkyl cellulose, etc., which can obtain high moldability due to excellent plasticity and water retention. Specifically, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose and hydroxypropyl methyl cellulose which are generally commercially available are suitable. The viscosity of the cellulose binder is 20 ° C., and a 1% aqueous solution measured with a B-type viscometer shows a suitability of 100 to 40,000 mPa · s. Among them, a cellulose binder exhibiting a high viscosity of 8000 to 40000 mPa · s. Cellulose-based binders exhibiting a relatively high aqueous solution viscosity are most preferred from the viewpoint that the amount used can be reduced because high shape retention can be introduced into the molding system due to excellent plasticity and water retention. The addition amount of the cellulosic binder for obtaining an extruded product exhibiting excellent fluidity and shape retention is generally about 0.1 to 10.0% by weight with respect to the total amount of the hydraulic substance, aggregate and the like. However, the amount added is preferably about 0.2 to 3.0% by weight in view of cost and the like. If the amount of cellulose binder added is too small, sufficient fluidity and shape retention cannot be introduced into the system, so an excellent extruded product cannot be obtained, and if the amount of cellulose binder added is too large. This is because the cost is unnecessarily high.
本発明における押出成形用混和剤には、必要に応じてセルロース系バインダーに類似の成形性効果が期待できる他の水溶性バインダーを併せて使用することができる。他の水溶性バインダーとしてはカルボキシメチルセルロース、ヒドロキシプロピル化デンプン、キサンタンガム、グアガム、ポリビニルアルコール、ポリエチレンオキサイド、ポリアクリルアミド等が挙げられる。In the extrusion molding admixture according to the present invention, if necessary, other water-soluble binders that can be expected to have a moldability effect similar to that of the cellulose binder can be used together. Examples of other water-soluble binders include carboxymethyl cellulose, hydroxypropylated starch, xanthan gum, guar gum, polyvinyl alcohol, polyethylene oxide, polyacrylamide and the like.
本発明において用いる減水剤としては一般に市販されているポリカルボン酸系減水剤、ナフタレンスルホン酸ホルマリン縮合物系減水剤、メラミンスルホン酸ホルマリン縮合物系減水剤、リグニンスルホン酸系減水剤が使用できる。
上記の減水剤においてはナフタレンスルホン酸ホルマリン縮合物系減水剤、メラミンスルホン酸ホルマリン縮合物系減水剤が安全衛生面で指摘のあるホルマリンを製造原料として含むため、上記のホルマリンを製造原料として含まず単量体組成、重合体鎖長の検討により得られた押出成形物の養生時の凝結時間調節が可能である点や比較的他の減水剤に比べて減水分散効果の温度依存性が小さいことからポリカルボン酸系減水剤が望ましい。As the water reducing agent used in the present invention, commercially available polycarboxylic acid-based water reducing agents, naphthalenesulfonic acid formalin condensate water reducing agents, melamine sulfonic acid formalin condensate water reducing agents, and lignin sulfonic acid water reducing agents can be used.
In the above water reducing agent, naphthalenesulfonic acid formalin condensate water reducing agent and melamine sulfonic acid formalin condensate water reducing agent contain formalin as a manufacturing raw material, which is pointed out in terms of safety and health. It is possible to adjust the setting time during curing of the extruded product obtained by examining the monomer composition and polymer chain length, and the temperature dependence of the water-reducing dispersion effect is relatively small compared to other water-reducing agents. To polycarboxylic acid-based water reducing agents are desirable.
本発明に用いるノニオン系界面活性剤としては高級アルコールエチレンオキシド付加物、高級脂肪族エチレンオキシド付加物、ポリオキシエチレンソルビタンエステル、高級脂肪酸ソルビタンエステルらの単独もしくはそれらの組み合わせによる併用系が本発明時の押出成形時の減水剤と同様の効果が確認されることから使用が可能である。ゆえに押出成形時の流動性効果発現には減水剤、ノニオン系界面活性剤の単独使用、減水剤とノニオン系界面活性剤の併用使用いずれの場合においてもよい。優れた流動性、保形性を示す押出成形物を得るための押出成形用組成物に対する減水剤及び／またはノニオン系界面活性剤の添加量としては水硬性物質、骨材等の合計量に対して０．０５−５．０重量％程度が一般的に使用されるが、コスト等の面を考慮に入れると添加量としては０．１−３．０重量％程度が望ましい。減水剤、ノニオン系界面活性剤を併用する場合添加比率は上記範囲内であれば特に制限されるものではない。これら減水剤及び／またはノニオン系界面活性剤の減水分散効果を系内に導入することにより水硬性物質や骨材を安定に分散させ押出成形時の流動性に大きな効果が認められ、減水剤及び／またはノニオン系界面活性剤を用いない系と比較し製造時の押出速度の向上や生産時の押出圧の低下が確認されるものである。Nonionic surfactants used in the present invention include higher alcohol ethylene oxide adducts, higher aliphatic ethylene oxide adducts, polyoxyethylene sorbitan esters, higher fatty acid sorbitan esters, etc., alone or in combination with a combination thereof. Since the same effect as the water reducing agent at the time of molding is confirmed, it can be used. Therefore, the fluidity effect at the time of extrusion may be expressed by using either a water reducing agent or a nonionic surfactant alone, or a combined use of a water reducing agent and a nonionic surfactant. The amount of water reducing agent and / or nonionic surfactant added to the composition for extrusion to obtain an extruded product exhibiting excellent fluidity and shape retention is relative to the total amount of hydraulic substance, aggregate, etc. In general, about 0.05 to 5.0% by weight is generally used, but the amount added is preferably about 0.1 to 3.0% by weight in consideration of cost and the like. When a water reducing agent and a nonionic surfactant are used in combination, the addition ratio is not particularly limited as long as it is within the above range. By introducing the water-reducing and dispersing effect of these water reducing agents and / or nonionic surfactants into the system, it is possible to stably disperse hydraulic substances and aggregates, and to have a great effect on fluidity during extrusion molding. In comparison with a system that does not use a nonionic surfactant, an improvement in extrusion speed during production and a decrease in extrusion pressure during production are confirmed.
本発明における押出成形用混和剤に用いる消泡剤としては市販されているエチレンオキシド、プロピレンオキシドを主成分とするポリオキシアルキレン系消泡剤、鉱物油系消泡剤もしくは変性シリコーン系等が使用可能である。これら消泡剤の中では粉体状消泡剤や液状消泡剤の両方が使用することができる。これらの消泡剤を押出成形用混和剤中組成中に用いることで消泡剤の系内への気泡連衡性調整効果によりセルロース系バインダー、減水剤併用系において問題となった押出成形時の成形品の表面性や寸法変化等の保形性の点で著しい改善がみられる。上記の消泡剤を併用使用することも可能である。優れた押出成形物を得るための消泡剤の添加量としては水硬性物質、骨材等の合計量に対して０．００１−４．０重量％程度が必要であるが、コスト等の面を考慮に入れると添加量としては０．００２−２．０重量％程度が望ましい。消泡剤の添加量が少なすぎる場合は保形性を系内に導入できないことから優れた押出成形物を得ることができず、消泡剤の添加量が多すぎる場合は流動性が打ち消される程度まで気泡連衡性調整効果を発揮し押出成形が不能となるためである。As the antifoaming agent used in the admixture for extrusion in the present invention, commercially available ethylene oxide, polyoxyalkylene antifoaming agent mainly composed of propylene oxide, mineral oil antifoaming agent or modified silicone type can be used. It is. Among these antifoaming agents, both powdery antifoaming agents and liquid antifoaming agents can be used. By using these antifoaming agents in the composition of the extrusion admixture, molding during extrusion molding has become a problem in the cellulose-based binder and water-reducing agent combined system due to the effect of adjusting the foam integrity in the system of the antifoaming agent. Significant improvement is seen in terms of shape retention, such as surface properties and dimensional changes. It is also possible to use the antifoaming agent in combination. The amount of antifoaming agent added to obtain an excellent extrudate is about 0.001 to 4.0% by weight with respect to the total amount of hydraulic substance, aggregate, etc. Taking this into consideration, the amount added is preferably about 0.002 to 2.0% by weight. If the amount of antifoaming agent added is too small, shape retention cannot be introduced into the system, so an excellent extruded product cannot be obtained, and if the amount of antifoaming agent added is too large, fluidity is canceled out. This is because the effect of adjusting the cell affinity is exhibited to the extent that extrusion molding becomes impossible.
本発明における押出成形用混和剤に用いるシリカ粉末としては多孔質シリカ微粉末、シリカフラワー、シリカフューム、タルク、ベントナイト、雲母、ゼオライト、パーライト、高炉スラグ、フライアッシュ、ガラス、クレー等の一般的なシリカ系粉体が使用可能である。これらの中では比表面積が大きく吸油量に優れる多孔質シリカ微紛末の使用が望ましい。多孔質シリカ微粉末は含水珪酸、湿式シリカ、乾式シリカ、合成シリカ等の状態で各方面にて粉粒化剤として用いられているが、本発明においても最適なシリカ粉末の内の一つとして用いられる。多孔質シリカ微粉末の本発明における役割は液状の減水剤、消泡剤、ノニオン系界面活性剤の吸収による粉体化のため、多孔質シリカ微粉末の表面積の小さいものが適することよりＢＥＴ法による比表面積が５０−４００ｍ２／ｇ、コールターカウンター法による平均粒子径が３０μｍ以下の非晶質二酸化珪素含有量が９０重量％以上のものが好ましい。General silica such as porous silica fine powder, silica flour, silica fume, talc, bentonite, mica, zeolite, perlite, blast furnace slag, fly ash, glass, clay etc. System powders can be used. Among these, it is desirable to use a fine powder of porous silica having a large specific surface area and excellent oil absorption. Porous silica fine powder is used as a granulating agent in various directions in the state of hydrous silicic acid, wet silica, dry silica, synthetic silica, etc., but also as one of the optimal silica powders in the present invention Used. The role of the porous silica fine powder in the present invention is to form a powder by absorbing a liquid water reducing agent, antifoaming agent, and nonionic surfactant. A specific surface area of 50 to 400 m 2 / g, an average particle diameter of 30 μm or less by a Coulter counter method, and an amorphous silicon dioxide content of 90% by weight or more are preferable.
本発明において消泡剤として粉末状消泡剤を用いる場合は減水剤及び／又はノニオン系界面活性剤をシリカ粉末に吸収させ粉粒状とする必要がある。これらの減水剤及び／又はノニオン系界面活性剤とシリカ粉末による複合材の製造方法としては公知の製造方法を用いることができる。例えば減水剤及び／又はノニオン系界面活性剤の３０−８０重量％の水溶液を作成し攪拌機付き混合用ファイバーミキサーに加え、さらに粉末シリカを加えて攪拌を加え十分に減水剤及び／又はノニオン系界面活性剤水溶液をシリカ粉末に吸収させる。次いで得られた混合物を送風定温乾燥機等で乾燥後、ハンマーミル等を用いて粉砕し振動篩機等の分級工程を行った後減水剤及び／又はノニオン系界面活性剤とシリカ粉末による複合材とする製造方法である。また、以下に述べる製造方法でもよい。ナウタミキサー混合機、ヘンシェルミキサー混合機、リボンミキサー混合機等にあらかじめ脱水しておいた減水剤及び／又はノニオン系界面活性剤を系内に加え、さらにシリカ粉末を投入し攪拌下シリカ粉末に減水剤及び／又はノニオン系界面活性剤を吸収させる。シリカ粉末に減水剤及び／又はノニオン系界面活性剤を吸収させる際、減水剤及び／又はノニオン系界面活性剤が流動性を持つ液体状である必要がある。このため減水剤及び／又はノニオン系界面活性剤が室温で固体の場合、製造工程時系内温度を減水剤及び／又はノニオン系界面活性剤の軟化点以上まで上昇させる必要がある。吸収工程終了後、得られた生成物をハンマーミル等で粉砕し振動篩機等の分級工程を行った後減水剤及び／又はノニオン系界面活性剤とシリカ粉末による複合材とする製造方法である。シリカ粉末の吸油能力によるが減水剤及び／又はノニオン系界面活性剤とシリカ粉末の混合比率（減水剤及び／又はノニオン系界面活性剤とシリカ粉末：シリカ粉末）は１：０．５−１：９９で製造されるのが好ましく、より好ましくは１：０．８−１：９である。In the present invention, when a powdery antifoaming agent is used as the antifoaming agent, it is necessary to absorb the water reducing agent and / or the nonionic surfactant into the silica powder to form a powder. A known manufacturing method can be used as a method for manufacturing a composite material using these water reducing agents and / or nonionic surfactants and silica powder. For example, a 30-80% by weight aqueous solution of a water reducing agent and / or nonionic surfactant is prepared and added to a mixing fiber mixer with a stirrer, and further, silica powder is added and stirred to sufficiently reduce the water reducing agent and / or nonionic interface. The aqueous activator solution is absorbed into the silica powder. Next, the obtained mixture is dried with a constant temperature dryer or the like, pulverized with a hammer mill, etc., and subjected to a classification process such as a vibration sieve, and then a composite material comprising a water reducing agent and / or a nonionic surfactant and silica powder. This is a manufacturing method. Moreover, the manufacturing method described below may be used. Add water-reducing agent and / or nonionic surfactant dehydrated in advance to Nauta mixer, Henschel mixer, ribbon mixer, etc., and add silica powder. Absorbing agent and / or nonionic surfactant. When the water reducing agent and / or the nonionic surfactant is absorbed into the silica powder, the water reducing agent and / or the nonionic surfactant needs to be in a liquid state having fluidity. For this reason, when the water reducing agent and / or the nonionic surfactant is solid at room temperature, it is necessary to raise the temperature in the system during the production process to the softening point or higher of the water reducing agent and / or the nonionic surfactant. After completion of the absorption process, the obtained product is pulverized with a hammer mill, etc., and subjected to a classification process such as a vibration sieve machine, and then a production method for producing a composite of a water reducing agent and / or a nonionic surfactant and silica powder. . Depending on the oil absorption capacity of the silica powder, the mixing ratio of the water reducing agent and / or nonionic surfactant and silica powder (water reducing agent and / or nonionic surfactant and silica powder: silica powder) is 1: 0.5-1: 99, preferably 1: 0.8-1: 9.
本発明において消泡剤として液状消泡剤を用いる場合は減水剤及び／又はノニオン系界面活性剤と液状消泡剤をシリカ粉末に吸収させ粉粒状とする必要がある。これらの複合体の製造方法としては上記と同様の製造方法にて対応が可能であるが、減水剤及び／又はノニオン系界面活性剤、液状消泡剤、多孔質シリカ微粉末を含む混合状態で同時にシリカ粉末に吸収粉末化して目的の複合体を得る製法、減水剤及び／又はノニオン系界面活性剤と液状消泡剤を個別にシリカ粉末に吸収粉末化して目的の複合体を得る製法のどちらを選択してもよい。In the present invention, when a liquid antifoaming agent is used as the antifoaming agent, it is necessary to absorb the water reducing agent and / or the nonionic surfactant and the liquid antifoaming agent into the silica powder to form a powder. These composites can be produced by the same production method as described above, but in a mixed state containing a water reducing agent and / or a nonionic surfactant, a liquid antifoaming agent and a fine porous silica powder. Either the production method to obtain the desired composite by absorbing powder into silica powder at the same time, the production method to obtain the desired composite by absorbing water reducing agent and / or nonionic surfactant and liquid antifoaming agent individually into silica powder May be selected.
本発明における最終的なセメント押出成形用混和剤を得る方法としては上記の製造方法により得られた複合体とセルロース系バインダー等とをナウタミキサー混合機やリボンミキサー混合機を用いて均一混合することにより最終的なセメント押出成形用混和剤とする。As a method for obtaining the final admixture for cement extrusion in the present invention, the composite obtained by the above production method and the cellulose-based binder are uniformly mixed using a Nauta mixer mixer or a ribbon mixer mixer. To the final admixture for cement extrusion.
本発明により得られた押出成形用混和剤はセメント押出成形物に使用されるが、二水石膏、半水石膏を主成分とする石膏系成形物に対しても使用可能である。The admixture for extrusion obtained according to the present invention is used for cement extrusions, but can also be used for gypsum-based moldings mainly composed of dihydrate gypsum and hemihydrate gypsum.
本発明により得られた押出成形用混和剤は一般的なセメント押出組成物に添加される。セメント押出組成物としてはセメント材料に普通ポルトランドセメント、高炉セメント、早強セメント、フライアッシュセメント、アルミナセメント等が使用され、骨材には通常の珪砂等が使用される。また、必要に応じて成形物の強度向上用に安全衛生面で影響がなく使用可能なガラス繊維等の無機繊維、パルプ、ビニロン繊維、ポリプロピレン繊維などの有機繊維、軽量化材であるパーライト等の無機軽量骨材、ポリスチレン系等の有機発泡剤、有機質中空微小球等の有機軽量化材、さらには凝結時間調整剤である凝結遅延剤や凝結促進剤、流動化剤、分離低減剤、防錆剤、膨張剤、ポリマー混和剤、着色剤等を本発明に影響のでない範囲で必要により添加可能である。The extrusion admixture obtained according to the present invention is added to a general cement extrusion composition. As the cement extrusion composition, ordinary Portland cement, blast furnace cement, early strength cement, fly ash cement, alumina cement or the like is used as the cement material, and ordinary silica sand or the like is used as the aggregate. In addition, if necessary, there is no influence on safety and hygiene in terms of improving the strength of molded products, such as inorganic fibers such as glass fibers, organic fibers such as pulp, vinylon fibers, and polypropylene fibers, and pearlite that is a lightweight material. Inorganic lightweight aggregates, organic foaming agents such as polystyrene, organic lightening materials such as organic hollow microspheres, and further, setting retarders and setting accelerators that are setting time adjusting agents, fluidizing agents, separation reducing agents, rust prevention An agent, a swelling agent, a polymer admixture, a colorant, and the like can be added as necessary within a range not affecting the present invention.
以下に本発明について具体的に実施例等を挙げ説明を行うが、本発明は以下の実施例のみに限定されるものではない。Hereinafter, the present invention will be specifically described with reference to examples and the like, but the present invention is not limited to the following examples.
（１）シリカ粉末を用いた複合体の製造方法
表１に記載の添加剤固形分配合組成で減水剤及び／又はノニオン系界面活性剤及び／又は液状消泡剤の約６０重量％水溶液を作成し、あらかじめ多孔質微小シリカ粉末を加えてあるファイバーミキサー（松下電器産業製ＭＸ−Ｘ５３）に加え室温条件下１０分間攪拌を加えることにより粗大粒子を細かく粉砕させながら多孔質微小シリカ粉末に十分減水剤及び／又はノニオン系界面活性剤及び／又は液状消泡剤を吸収させた。攪拌終了後、送風定温乾燥機（東洋製作所製ＲＲＳ６２０ＤＡ）中で系内温度を８０℃に保ち十分乾燥させた後、１００メッシュの篩を通過させることにより目的とする複合体１−７を得た。なお、本発明に関する複合体の製造方法は上記製造方法に限定されるものではない。(1) Production method of composite using silica powder A 60% by weight aqueous solution of a water reducing agent and / or a nonionic surfactant and / or a liquid antifoaming agent is prepared with the additive solid content blending composition shown in Table 1. In addition to the fiber mixer (MX-X53 manufactured by Matsushita Electric Industrial Co., Ltd.) to which porous micro silica powder has been added in advance, the mixture is stirred for 10 minutes at room temperature to sufficiently reduce the water content of the porous micro silica powder while finely pulverizing coarse particles. An agent and / or a nonionic surfactant and / or a liquid antifoaming agent was absorbed. After completion of the stirring, the system temperature was kept at 80 ° C. in a blowing constant temperature dryer (Toyo Seisakusho RRS620DA), and the mixture was sufficiently dried, and then passed through a 100 mesh sieve to obtain the intended composite 1-7. . In addition, the manufacturing method of the composite body regarding this invention is not limited to the said manufacturing method.
添加剤２：マイテイ３０００Ｓ（減水剤；花王製：ポリカルボン酸系減水剤）
添加剤３：ＭＹＬ−１０（ノニオン系界面活性剤；日光ケミカルズ製：ラウリン酸ポリエチレングリコール）
添加剤４：プルロニックＬ−６１（液状消泡剤；旭電化製：ポリオキシアルキレン系消泡剤）
添加剤５：カープレックス＃８０（多孔質微小シリカ粉末；シオノギ製薬製：平均粒子径０．０２３μｍ、比表面積１９３ｍ２／ｇ）
Additive 2: Mighty 3000S (water reducing agent; manufactured by Kao: polycarboxylic acid-based water reducing agent)
Additive 3: MYL-10 (nonionic surfactant; manufactured by Nikko Chemicals: polyethylene glycol laurate)
Additive 4: Pluronic L-61 (liquid antifoaming agent; manufactured by Asahi Denka: polyoxyalkylene-based antifoaming agent)
Additive 5: Carplex # 80 (porous micro silica powder; manufactured by Shionogi Pharmaceutical Co., Ltd .: average particle size 0.023 μm, specific surface area 193 m 2 / g)
（２）セメント押出成形評価
上記に述べた複合体１−７を用いた本発明である押出成形用混和剤を用いて行ったセメント押出成形評価結果を実施例１−９として、本発明品を用いないセメント押出成形評価結果を比較例１−５として表２、表３に示すが本発明はこれらに限定されるものではない。また、セメント押出成形評価を行った際使用した材料は以下のものを使用し評価を行った。
（１）セメント：普通ポルトランドセメント（住友大阪セメント製）
（２）骨材（珪砂）：シリカフラワー＃２００（瑞浪シリカ製）
（３）軽量骨材（パーライト）：ハットリパーライト（ハットリ製）
（４）ポリプロピレン繊維：ＰＺＬ（大和紡績製）
（５）故紙解砕物：ＰＳ（日本製紙製）
（６）セルロース系バインダー：マーポローズＭＥ−３０００００（松本油脂製薬製：ヒドロキシエチルメチルセルロース（２０℃１重量％水溶液粘度１０３００ｍＰａ・ｓ（Ｂ型粘度計３０ｒｐｍ）））
（７）粉末消泡剤：ＳＮデフォーマー１４ＨＰ（サンノプコ製：ポリエーテル系消泡剤）
（８）減水剤：マリアリムＡ−２０（減水剤；日本油脂（株）ポリアルキレングリコールアルケニルエーテル−無水マレイン酸系誘導体にてなるポリカルボン酸系減水剤）
（９）水：水道水
（１０）複合物１−７：本発明品(2) Evaluation of Cement Extrusion Cement Extrusion Evaluation using the admixture for extrusion molding of the present invention using the composite 1-7 described above was used as Example 1-9, and the product of the present invention was used as Example 1-9. The results of evaluation of cement extrusion molding not used are shown in Tables 2 and 3 as Comparative Examples 1-5, but the present invention is not limited to these. Moreover, the materials used when the cement extrusion molding evaluation was performed were evaluated using the following materials.
(1) Cement: Ordinary Portland cement (manufactured by Sumitomo Osaka Cement)
(2) Aggregate (silica sand): Silica flower # 200 (made by Mizunami Silica)
(3) Lightweight aggregate (perlite): Hatri perlite (made by Hattori)
(4) Polypropylene fiber: PZL (Daiwabo)
(5) Waste paper crushed material: PS (manufactured by Nippon Paper Industries)
(6) Cellulose-based binder: Marporose ME-300000 (Matsumoto Yushi Seiyaku Co., Ltd .: hydroxyethyl methylcellulose (20 ° C., 1 wt% aqueous solution viscosity 10300 mPa · s (B-type viscometer 30 rpm)))
(7) Powder antifoaming agent: SN deformer 14HP (manufactured by San Nopco: polyether antifoaming agent)
(8) Water reducing agent: Marialim A-20 (water reducing agent; polycarboxylic acid water reducing agent comprising polyalkylene glycol alkenyl ether-maleic anhydride derivative)
(9) Water: Tap water (10) Composite 1-7: Product of the present invention
セメント押出成形評価としては以下の押出製造方法により成形物を作成し、表２、３に記載のセメント押出成形評価を行った。As the cement extrusion molding evaluation, a molded product was prepared by the following extrusion manufacturing method, and the cement extrusion molding evaluation described in Tables 2 and 3 was performed.
押出成形板製造方法
水以外の材料をレディゲミキサー（マツボー製Ｍ２０）内に入れ、５分間攪拌を加え十分に混合した。次いで所定量の水を２分間で噴霧することによりセメント押出成形評価用材料を全て混合した。実施例１−９に用いる押出成形用混和剤はあらかじめセルロース系バインダー、粉末消泡剤、複合物１−７を所定の割合で均一に混合したものを用いた。また、比較例４，５で使用した減水剤は水溶液のためレディゲミキサー内で水を噴霧して混合する際に水にあらかじめ加え、水量を調節の上噴霧した。混合終了後、１０Ｌの双腕ニーダー（本田鉄工製ＨＢＮ−１０Ｄ）にて３分間で十分混合を行った後、粘土様の高粘性物質を作成した。得られた粘土様の高粘性物質を真空押出成形機（本田鉄工製ＤＥ−５０Ｄ）を用いて押出成形しセメント成形板を作成した。なお、真空押出成形機の系内温度を３０℃真空度−０．０９６ＭＰａ以下に保ちダイス形状は４０ｍｍ×１０ｍｍを使用し平板状の成形板を得た。この際、表２、３に記載のセメント押出成形に関する表面状態、吐出状態等の評価を行った。得られたセメント成形板を７０℃で１２時間一次養生を行い、さらに１７０℃で１０時間オートクレーブ養生を行った後、養生後のセメント成形板を用いて表２、３に記載のセメント成形板に関する曲げ強度の測定を行った。なお、押出成形板製造並びに押出成形板に関する評価は室温を２５℃に、湿度を３０％に保たれた室内にて作業を行った。Extruded plate manufacturing method Materials other than water were placed in a Redige mixer (M20, manufactured by Matsubo) and mixed thoroughly by stirring for 5 minutes. Subsequently, the cement extrusion molding evaluation materials were all mixed by spraying a predetermined amount of water for 2 minutes. As the admixture for extrusion used in Example 1-9, a cellulose binder, a powder antifoaming agent, and a composite 1-7 were previously mixed uniformly at a predetermined ratio. Further, since the water reducing agent used in Comparative Examples 4 and 5 was an aqueous solution, when water was sprayed and mixed in a Redige mixer, it was added in advance to the water and sprayed after adjusting the amount of water. After mixing, the mixture was sufficiently mixed for 3 minutes with a 10 L double-arm kneader (HBN-10D manufactured by Honda Iron Works), and then a clay-like high-viscosity material was prepared. The obtained clay-like high-viscosity substance was extruded using a vacuum extrusion molding machine (DE-50D manufactured by Honda Iron Works) to prepare a cement-molded plate. In addition, the system temperature of the vacuum extrusion molding machine was kept at 30 ° C. and the vacuum degree was −0.096 MPa or less, and the die shape was 40 mm × 10 mm to obtain a flat molded plate. At this time, the surface state, the discharge state and the like related to the cement extrusion molding described in Tables 2 and 3 were evaluated. The obtained cement-molded plate is subjected to primary curing at 70 ° C. for 12 hours, and further subjected to autoclave curing at 170 ° C. for 10 hours. The bending strength was measured. In addition, the evaluation regarding extrusion-molded board manufacture and an extrusion-molded board performed work in the room | chamber interior which maintained room temperature at 25 degreeC and 30% of humidity.
表面状態評価方法
セメント押出成形時にダイスより押出されるセメント成形板を目視により観察し以下の評価基準により表面状態の評価を行った。
○：セメント成形板の表面が平滑で良好
△：セメント成形板の表面に凹凸がやや見られる。
×：セメント成形板の表面に凹凸が見られる。もしくはセメント成形板にひび割れが見られる。Surface Condition Evaluation Method A cement molded plate extruded from a die at the time of cement extrusion was visually observed, and the surface condition was evaluated according to the following evaluation criteria.
○: The surface of the cement molded plate is smooth and good. Δ: The surface of the cement molded plate is slightly uneven.
X: Unevenness is observed on the surface of the cement-molded plate. Or cracks are seen in the cement molded board.
吐出状態評価方法
セメント押出成形時にダイスより押出されるセメント成形板を目視により観察し以下の評価基準により吐出状態の評価を行った。
○：セメント成形板が安定に真っ直ぐに押出される
△：セメント成形板が押出される際やや押出速度に変化が見られる。
×：セメント成形板が押出される際押出速度に変化が見られ安定にセメント成形板が押出されない。Discharge state evaluation method The cement molded plate extruded from the die during cement extrusion molding was visually observed, and the discharge state was evaluated according to the following evaluation criteria.
○: The cement-molded plate is extruded straight and stably Δ: When the cement-molded plate is extruded, there is a slight change in the extrusion speed.
X: When the cement molded plate is extruded, a change is observed in the extrusion speed, and the cement molded plate is not stably extruded.
寸法精度評価方法
セメント押出成形時にダイスより押出されたセメント成形板の寸法を精査しダイス寸法と比較することにより以下の評価基準により寸法精度の評価を行った。
○：セメント成形板の幅、厚みの誤差が共に０．２ｍｍ以下
△：セメント成形板の幅、厚みの誤差が共に０．２ｍｍ以上０．３ｍｍ以下
×：セメント成形板の幅、厚みの誤差が共に０．３ｍｍ以上Dimensional accuracy evaluation method The dimensional accuracy was evaluated according to the following evaluation criteria by examining the dimensions of the cement-molded plate extruded from the die during cement extrusion and comparing it with the die size.
○: Both the width and thickness errors of the cement-molded plate are 0.2 mm or less. Δ: Both the width and thickness errors of the cement-formed plate are 0.2 mm or more and 0.3 mm or less. Both 0.3mm or more
押出圧評価方法
セメント押出成形時に真空押出成形機に取り付けてある圧力計を目視により観察し押出圧の評価を行った。Extrusion pressure evaluation method The extrusion pressure was evaluated by visually observing a pressure gauge attached to the vacuum extrusion molding machine during cement extrusion.
押出速度評価方法
セメント押出成形時に真空押出成形機より押出される際のセメント成形板の流れる速度を測定し押出速度の評価を行った。Extrusion rate evaluation method The extrusion rate was evaluated by measuring the flow rate of the cement-formed plate when extruded from a vacuum extruder during cement extrusion.
押出成形物硬度評価方法
セメント押出成形時にダイスより押出されたセメント成形板をクレー硬度計（日本碍子製）を用いて硬度を測定することにより押出成形物硬度評価の評価を行った。なお、表２、３に記載の数値が高いほど硬度が高いものを示す。Extruded Product Hardness Evaluation Method Extruded product hardness evaluation was evaluated by measuring the hardness of a cement molded plate extruded from a die during cement extrusion using a clay hardness meter (manufactured by Nippon Choshi Co., Ltd.). In addition, the thing whose hardness is so high that the numerical value of Tables 2 and 3 is high is shown.
曲げ強度評価方法
オートクレーブ養生後のセメント成形板をＪＩＳ Ｒ５２０１の評価方法に準じて測定を行い曲げ強度の評価を行った。Bending strength evaluation method The cement-molded plate after curing in an autoclave was measured according to the evaluation method of JIS R5201, and the bending strength was evaluated.
表２、３より明らかなように従来の押出成形用混和剤を用いて押出成形を行った場合（比較例１−５）に比べて、本発明品を用いて押出成形を行った場合（実施例１−９）はハンドリング面に優れかつ押出成形時における流動性、押出成形物の保形性に優れることが確認された。As is clear from Tables 2 and 3, when extrusion molding was performed using the product of the present invention as compared to the case where extrusion molding was performed using the conventional additive for extrusion molding (Comparative Example 1-5) (implementation) It was confirmed that Example 1-9) was excellent in handling surface, fluidity during extrusion molding, and excellent shape retention of the extruded product.
本発明はあらかじめ減水剤及び／又はノニオン系界面活性剤、消泡剤を必要に応じてシリカ粉末に吸着させ粉粒状としセルロース系バインダーに混合した組成物を含む粉体状のセメント押出成形用混和剤である。本発明品はセメント押出成形用混和剤として使用する際、粉体として取り扱いに簡単で安価にセメント押出成形することができ、かつ従来技術に比べて優れた押出成形時の流動性や押出成形物の保形性を系内に導入することができる新規なセメント押出成形用混和剤である。The present invention is a powdered cement extrusion blend containing a composition in which a water reducing agent and / or a nonionic surfactant and an antifoaming agent are adsorbed on silica powder as needed and mixed with a cellulose binder. It is an agent. When the product of the present invention is used as an admixture for cement extrusion, it is easy to handle as a powder and can be cement-extruded at low cost, and has superior fluidity and extrusion molding during extrusion compared to the prior art. It is a novel admixture for cement extrusion that can introduce the shape-retaining property into the system.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012079095A3 (en) * | 2010-12-10 | 2012-12-06 | Troy Corporation | Adhesive strength enhancers for cementitious compositions |
| JP2014133663A (en) * | 2013-01-08 | 2014-07-24 | Matsumoto Yushi Seiyaku Co Ltd | Admixture for cement extrusion molding and its use |
| EP2686282B1 (en) * | 2011-03-14 | 2018-05-02 | Evonik Degussa GmbH | Mineral building material compositions |
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| CN109721275A (en) * | 2019-03-06 | 2019-05-07 | 西安同成建筑科技有限责任公司 | A kind of dedicated brightener of concrete and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221354A (en) * | 1984-04-16 | 1985-11-06 | 昭和電工株式会社 | Cement admixture |
| JPH05301751A (en) * | 1992-04-24 | 1993-11-16 | Taisei Corp | Complex cement admixture |
| JPH06182749A (en) * | 1992-12-22 | 1994-07-05 | Matsushita Electric Works Ltd | Manufacture of cement cured body |
| JPH10226550A (en) * | 1997-02-10 | 1998-08-25 | Nof Corp | Additive composition for cement |
-
2005
- 2005-02-22 JP JP2005084749A patent/JP4937517B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60221354A (en) * | 1984-04-16 | 1985-11-06 | 昭和電工株式会社 | Cement admixture |
| JPH05301751A (en) * | 1992-04-24 | 1993-11-16 | Taisei Corp | Complex cement admixture |
| JPH06182749A (en) * | 1992-12-22 | 1994-07-05 | Matsushita Electric Works Ltd | Manufacture of cement cured body |
| JPH10226550A (en) * | 1997-02-10 | 1998-08-25 | Nof Corp | Additive composition for cement |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012079095A3 (en) * | 2010-12-10 | 2012-12-06 | Troy Corporation | Adhesive strength enhancers for cementitious compositions |
| US8529693B2 (en) | 2010-12-10 | 2013-09-10 | Troy Corporation | Adhesive strength enhancers for cementitious compositions |
| GB2504394A (en) * | 2010-12-10 | 2014-01-29 | Troy Corp | Adhesive strength enhancers for cementitious compositions |
| GB2504394B (en) * | 2010-12-10 | 2019-07-03 | Troy Corp | Adhesive strength enhancers for cementitious compositions |
| EP2686282B1 (en) * | 2011-03-14 | 2018-05-02 | Evonik Degussa GmbH | Mineral building material compositions |
| JP2014133663A (en) * | 2013-01-08 | 2014-07-24 | Matsumoto Yushi Seiyaku Co Ltd | Admixture for cement extrusion molding and its use |
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