JP5192343B2 - Method for producing hydraulic composition - Google Patents
Method for producing hydraulic composition Download PDFInfo
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- JP5192343B2 JP5192343B2 JP2008258778A JP2008258778A JP5192343B2 JP 5192343 B2 JP5192343 B2 JP 5192343B2 JP 2008258778 A JP2008258778 A JP 2008258778A JP 2008258778 A JP2008258778 A JP 2008258778A JP 5192343 B2 JP5192343 B2 JP 5192343B2
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- glycerin
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- 239000000203 mixture Substances 0.000 title claims description 66
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 116
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000000178 monomer Substances 0.000 claims description 73
- 235000011187 glycerol Nutrition 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 34
- 238000010298 pulverizing process Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 239000004568 cement Substances 0.000 claims description 24
- -1 alkali metal salt Chemical class 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 238000000227 grinding Methods 0.000 description 48
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 230000032683 aging Effects 0.000 description 16
- 239000004567 concrete Substances 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000010440 gypsum Substances 0.000 description 8
- 229910052602 gypsum Inorganic materials 0.000 description 8
- 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 7
- 239000000463 material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001669 calcium Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- DHUSXRNOMZWNNA-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCS(O)(=O)=O DHUSXRNOMZWNNA-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- FBKBIOOBMXQNBA-UHFFFAOYSA-N propane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)S(O)(=O)=O FBKBIOOBMXQNBA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、水硬性組成物の製造方法に関する。 The present invention relates to a method for producing a hydraulic composition.
水硬性化合物、例えばポルトランドセメントクリンカー、高炉スラグ等を粉砕して種々の水硬性粉体が製造されている。例えば、ポルトランドセメントは、石灰石、粘土、鉄さい等の原料を焼成して得られたクリンカーに適量の石膏を加え、粉砕して製造される。その際、粉砕効率を上げるために、ジエチレングリコールやトリエタノールアミンなどの粉砕助剤が用いられている。粉砕工程においては水硬性化合物をできるだけ能率良く所望の粒径にすることが望ましい。このため、従来、粉砕工程において粉砕助剤を使用することが行われている。 Various hydraulic powders are produced by pulverizing hydraulic compounds such as Portland cement clinker and blast furnace slag. For example, Portland cement is produced by adding an appropriate amount of gypsum to a clinker obtained by firing raw materials such as limestone, clay, iron slag and the like and then pulverizing them. At that time, in order to increase the grinding efficiency, grinding aids such as diethylene glycol and triethanolamine are used. In the pulverization step, it is desirable that the hydraulic compound is made as efficiently as possible with the desired particle size. For this reason, conventionally, a grinding aid is used in the grinding step.
粉砕助剤としては、プロピレングリコールやジエチレングリコールなどの低級アルキレングリコールのオリゴマー、トリエタノールアミンなどのアルカノールアミン類等が知られている。また、例えば、特許文献１では、球形炭酸カルシウムを粉砕する際に添加する粉砕助剤としてグリセリンを用いることが開示されている。特許文献２ではセメントクリンカーの粉砕助剤としてリグニンスルホン酸塩とグリセリンを併用することが開示されている。さらに特許文献２には、グリセリン単独では粉砕助剤として効果が小さく実用されていないことも述べられている。特許文献３には、アルカリ金属塩を含有する未処理グリセリンをクリンカーの粉砕工程に添加することが開示されている。 Known grinding aids include oligomers of lower alkylene glycols such as propylene glycol and diethylene glycol, alkanolamines such as triethanolamine, and the like. For example, Patent Document 1 discloses that glycerin is used as a grinding aid to be added when grinding spherical calcium carbonate. Patent Document 2 discloses that lignin sulfonate and glycerin are used in combination as a grinding aid for cement clinker. Furthermore, Patent Document 2 also states that glycerin alone is not effective as a grinding aid and is not practically used. Patent Document 3 discloses that untreated glycerin containing an alkali metal salt is added to a clinker grinding step.
コンクリート製品は、セメント、骨材、水、及び分散剤（減水剤）等の材料を混練し、様々な型枠に打設し、養生（硬化）工程を経て製品化される。コンクリート製品では、養生工程後の脱型時の製品表面に気泡、充填不足等が原因と思われる窪みが生じたり、その他種々要因により表面美観の低下が生じると、その商品価値を下げることになる。表面美観が低下したコンクリート製品については、脱型後に手作業による補修をおこなっているのが現状である。しかし、この作業には多くの人手と時間を要する為、製造コスト上昇原因の一つに挙げられている。 Concrete products are kneaded with materials such as cement, aggregate, water, and a dispersant (water reducing agent), placed in various molds, and commercialized through a curing (hardening) process. In concrete products, if the surface of the product is removed after the curing process, the product surface will be lowered if there is a dent that seems to be caused by bubbles or insufficient filling, or if the surface aesthetics deteriorate due to various other factors. . At present, concrete products with reduced surface aesthetics are repaired manually after demolding. However, since this work requires a lot of manpower and time, it is listed as one of the causes of increased manufacturing costs.
コンクリート製品の表面美観への影響因子として様々なものが知られているが、中でも（１）混練時に発生する気泡の量や質、（２）脱型時のコンクリート強度、（３）コンクリート粘性が重要な因子といわれている。 Various factors are known as factors affecting the surface aesthetics of concrete products. Among them, (1) the amount and quality of bubbles generated during kneading, (2) concrete strength during demolding, and (3) concrete viscosity It is said to be an important factor.
コンクリート製品の製造にあたっては、未硬化状態での流動性が良好で、硬化体強度に優れることが望まれる。特許文献４には、セメント組成物の流動性低下が少なく、初期材齢に高い強度を発現することができる、グリセリン又はグリセリン誘導体とポリオキシアルキレン化合物を側鎖に有するポリカルボン酸系共重合体とを含有するセメント用強度向上剤が開示されている。 In the production of concrete products, it is desired that the fluidity in an uncured state is good and the cured body strength is excellent. Patent Document 4 discloses a polycarboxylic acid-based copolymer having glycerin or a glycerin derivative and a polyoxyalkylene compound in the side chain, which can reduce the fluidity of the cement composition and exhibit high strength at an early age. A cement strength improver containing
水硬性化合物の粉砕助剤として広く使用されているジエチレングリコールは、安全面や健康面への影響に配慮しながら使用する必要があり、使用上の制約が大きい物質である。また、トリエタノールアミンも、化学兵器禁止法の第二種指定物質該当品目に指定されていることから、今後、使用制限を受ける可能性があり、代替できる物質を見出すことが望まれる。 Diethylene glycol, which is widely used as a grinding aid for hydraulic compounds, needs to be used while taking into account its impact on safety and health, and is a material with great restrictions on use. Triethanolamine is also designated as a Class 2 Designated Substance in the Chemical Weapons Prohibition Law, so it may be subject to use restrictions in the future, and it is desirable to find a substitute substance.
本発明の課題は、安全性の高い製造工程を有し、初期材齢に高い強度を発現することができる水硬性組成物を与える水硬性組成物の製造方法を提供することである。 The subject of this invention is providing the manufacturing method of the hydraulic composition which has a highly safe manufacturing process and gives the hydraulic composition which can express high intensity | strength at an early age.
本発明は、グリセリンと水及び／又は炭素数１〜４の１価アルコールとの存在下で水硬性化合物を粉砕して得られる水硬性粉体と、
下記の一般式（１）で表される単量体由来の構成単位１と下記の一般式（２）で表される単量体由来の構成単位２とを有する重合体と、
水と、
を混合して、水硬性組成物を得る、水硬性組成物の製造方法であり、
前記水硬性化合物の粉砕の際の、グリセリンの存在量が、水硬性化合物１００重量部に対して、０．００１〜０．２重量部であり、水及び／又は炭素数１〜４の１価アルコールの存在量が、水硬性化合物１００重量部に対して、０．００１〜０．２重量部である、水硬性組成物の製造方法に関する。
The present invention provides a hydraulic powder obtained by pulverizing a hydraulic compound in the presence of glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms,
A polymer having a structural unit 1 derived from a monomer represented by the following general formula (1) and a structural unit 2 derived from a monomer represented by the following general formula (2);
water and,
Is a method for producing a hydraulic composition, to obtain a hydraulic composition,
The amount of glycerin in the pulverization of the hydraulic compound is 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the hydraulic compound, and water and / or monovalent having 1 to 4 carbon atoms. The present invention relates to a method for producing a hydraulic composition, wherein the abundance of alcohol is 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the hydraulic compound.
〔式中、Ｒ1、Ｒ2は、それぞれ水素原子又はメチル基、Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4、ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基、ｐは０又は１の数、ｑは０〜２の数、ｒはＡＯの平均付加モル数であり、３〜３００の数、Ｒ4は水素原子又は炭素数１〜１８のアルキル基を表す。〕 [In the formula, R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 is a hydrogen atom, or — (CH 2 ) q (CO) p O (AO) r R 4 , and AO has 2 to 4 carbon atoms. Oxyalkylene group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R 4 is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]
〔式中、Ｒ5〜Ｒ7は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよく、その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の数を表す。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属（1/2原子）、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基を表す。〕 Wherein, R 5 to R 7 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or another (CH 2) s COOM 2 and anhydrous In this case, M 1 and M 2 of those groups are not present. s represents the number of 0-2. M 1 and M 2 each represent a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
本発明によれば、安全性の高い製造工程により、初期材齢に高い強度を発現することができる水硬性組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the hydraulic composition which can express high intensity | strength at an early age is provided by a highly safe manufacturing process.
本発明では、水硬性粉体の製造の際にグリセリンと水及び／又は炭素数１〜４の１価アルコールとを水硬性化合物に対する粉砕助剤として用いる。 In the present invention, glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms are used as a grinding aid for the hydraulic compound during the production of the hydraulic powder.
粉砕助剤としてグリセリンと水及び／又は炭素数１〜４の１価アルコールとを用いて得られた水硬性粉体に対し、ポリアルキレンオキサイドのグラフト鎖を有する特定のポリカルボン酸系重合体を分散剤として用いる場合、粉砕助剤としてジエチレングリコールを用いたときよりも初期材齢が高い水硬性組成物が得られる。この理由の詳細は不明であるが、グリセリンと水及び／又は炭素数１〜４の１価アルコールとを用いることで、得られた水硬性化合物（水硬性粉体）上に存在するグリセリンと、特定のポリカルボン酸系重合体との複合効果により適度なカルシウムキレート力が得られるために、水和反応が進行し、初期材齢強度が高くなると推定される。このカルシウムキレート力が強すぎる場合は、水硬性化合物（水硬性粉体）の水和反応が阻害され、硬化遅延を生じて初期材齢強度が低下する。逆にカルシウムキレート力が弱すぎる場合は、水和反応の向上効果がなく初期材齢強度も向上しないと推定される。また、水硬性化合物の粉砕の際に水を併用してもグリセリンの保水効果により、水硬性化合物（水硬性粉体）の水和反応は進行せず、かつグリセリンの粘度を低下でき、グリセリンと水の併用で粉砕助剤として好適に使用できる。そして、水硬性化合物の粉砕の際に炭素数１〜４の１価アルコールを併用した場合も、グリセリンの粘度を低下でき、グリセリンと該アルコールの併用で粉砕助剤として好適に使用できると推定される。 For a hydraulic powder obtained using glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms as a grinding aid, a specific polycarboxylic acid polymer having a polyalkylene oxide graft chain is used. When used as a dispersant, a hydraulic composition having a higher initial age than that obtained when diethylene glycol is used as a grinding aid can be obtained. Although the details of this reason are unclear, by using glycerin and water and / or monohydric alcohol having 1 to 4 carbon atoms, glycerin present on the obtained hydraulic compound (hydraulic powder), It is presumed that the hydration reaction proceeds and the initial age strength is increased because an appropriate calcium chelating power is obtained by the combined effect with a specific polycarboxylic acid polymer. When this calcium chelating power is too strong, the hydration reaction of the hydraulic compound (hydraulic powder) is inhibited, causing a delay in curing and lowering the initial age strength. Conversely, when the calcium chelate strength is too weak, it is estimated that there is no effect of improving the hydration reaction and the initial age strength is not improved. In addition, even when water is used in combination with the pulverization of the hydraulic compound, the hydration reaction of the hydraulic compound (hydraulic powder) does not proceed due to the water retention effect of glycerin, and the viscosity of glycerin can be reduced. It can be suitably used as a grinding aid in combination with water. And even when a monohydric alcohol having 1 to 4 carbon atoms is used in combination with the pulverization of the hydraulic compound, it is estimated that the viscosity of glycerin can be lowered, and the combined use of glycerin and the alcohol can be suitably used as a pulverization aid. The
本発明では、グリセリンと、水及び／又は炭素数１〜４の１価アルコール（以下、グリセリン系粉砕助剤と称する）との存在下で水硬性化合物を粉砕して得られる水硬性粉体が用いられる。グリセリンは、塩析によるグリセリン水溶液の保存安定性の面から、アルカリ金属塩が除去された精製グリセリンであることが好ましく、グリセリン中のアルカリ金属塩の含有量が１重量％未満であることがより好ましく、０．１重量％以下がさらに好ましく、実質的に含まないことがよりさらに好ましい。 In the present invention, a hydraulic powder obtained by pulverizing a hydraulic compound in the presence of glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms (hereinafter referred to as glycerin-based pulverization aid) is provided. Used. The glycerin is preferably purified glycerin from which the alkali metal salt has been removed from the viewpoint of storage stability of the glycerin aqueous solution by salting out, and the content of the alkali metal salt in the glycerin is preferably less than 1% by weight. Preferably, it is more preferably 0.1% by weight or less, and still more preferably substantially not contained.
通常、ポルトランドセメントは、石灰石、粘土、鉄さい等の原料を焼成して得られた水硬性化合物であるクリンカー（セメントクリンカーともいい、石膏が入っている場合もある。通常、粒径１ｃｍ程度。）を最大３ｍｍ程度に粉砕し（予備粉砕）、適量の石膏を加え、さらに十数μｍまで粉砕して（仕上粉砕）、ブレーン値２５００ｃｍ2／ｇ以上の比表面積を有する粉体として製造される。本発明に係るグリセリン系粉砕助剤は、前記粉砕の際の粉砕助剤として、好適には仕上粉砕での粉砕助剤として用いられる。 Usually, Portland cement is a clinker (also called cement clinker, which is a hydraulic compound obtained by firing raw materials such as limestone, clay, iron slag, etc., and sometimes contains gypsum. Usually, particle size is about 1 cm. ) To a maximum of about 3 mm (preliminary pulverization), an appropriate amount of gypsum is added, and further pulverized to a dozen μm (finish pulverization) to produce a powder having a specific surface area of a brain value of 2500 cm 2 / g or more. . The glycerin-based grinding aid according to the present invention is used as a grinding aid for the grinding, preferably as a grinding aid for finish grinding.
本発明に係るグリセリン系粉砕助剤のうちグリセリンは、初期強度発現の観点から、水硬性化合物１００重量部、なかでもセメントクリンカー１００重量部に対して、０．００１〜０．２重量部、好ましくは０．０１〜０．１重量部、さらに好ましくは０．０２〜０．０５重量部用いられる。 Among the glycerin-based grinding aids according to the present invention, glycerin is 0.001 to 0.2 parts by weight, preferably 100 to 100 parts by weight of a hydraulic compound, particularly 100 parts by weight of cement clinker, from the viewpoint of developing initial strength. Is used in an amount of 0.01 to 0.1 parts by weight, more preferably 0.02 to 0.05 parts by weight.
また、本発明に係るグリセリン系粉砕助剤のうち水及び／又は炭素数１〜４の１価アルコールは、水硬性化合物への添加しやすさを向上する観点から、水硬性化合物１００重量部、なかでもセメントクリンカー１００重量部に対して、０．００１〜０．２重量部、好ましくは０．００５〜０．１重量部、さらに好ましくは０．０２〜０．０５重量部用いられる。 In addition, water and / or a monohydric alcohol having 1 to 4 carbon atoms in the glycerin-based grinding aid according to the present invention is 100 parts by weight of a hydraulic compound from the viewpoint of improving ease of addition to the hydraulic compound, Among these, 0.001 to 0.2 parts by weight, preferably 0.005 to 0.1 parts by weight, and more preferably 0.02 to 0.05 parts by weight is used with respect to 100 parts by weight of cement clinker.
グリセリンと、水及び／又は炭素数１〜４の１価アルコールとの重量比は、水硬性化合物への添加しやすさと水硬性組成物の初期強度発現の観点から、グリセリン／（水及び／又は炭素数１〜４の１価アルコール）で９０／１０〜５０／５０、さらに８５／１５〜５０／５０、よりさらに７５／２５〜５０／５０であることが好ましい。 The weight ratio of glycerin to water and / or a monohydric alcohol having 1 to 4 carbon atoms is glycerin / (water and / or from the viewpoint of easy addition to the hydraulic compound and expression of the initial strength of the hydraulic composition. The monohydric alcohol having 1 to 4 carbon atoms is preferably 90/10 to 50/50, more preferably 85/15 to 50/50, and even more preferably 75/25 to 50/50.
また、水硬性化合物の粉砕の際の、グリセリンと水及び／又は炭素数１〜４の１価アルコールとの合計の存在量は、水硬性化合物１００重量部、なかでもクリンカー１００重量部に対して、０．００１〜０．２重量部、さらに０．００５〜０．１重量部であることが好ましい。 In addition, the total amount of glycerin and water and / or monohydric alcohol having 1 to 4 carbon atoms in the pulverization of the hydraulic compound is 100 parts by weight of the hydraulic compound, especially 100 parts by weight of the clinker. 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.1 parts by weight.
水硬性化合物の粉砕、なかでも仕上粉砕は、水硬性化合物、なかでもクリンカーを含む原料に粉砕助剤を添加して行うことが好ましい。添加する方法としては、粉砕助剤の液状物、もしくは粉砕助剤と他の成分とを含む液状混合物を、滴下、噴霧等により水硬性化合物に供給する方法が挙げられる。 The pulverization of the hydraulic compound, particularly the finish pulverization, is preferably performed by adding a pulverization aid to the raw material containing the hydraulic compound, particularly clinker. Examples of the method of adding include a method of supplying a liquid compound of a grinding aid or a liquid mixture containing the grinding aid and other components to the hydraulic compound by dropping, spraying, or the like.
本発明に係るグリセリン系粉砕助剤は、取扱い性、及び水硬性粉体の風化（空気中の水分との反応や炭酸化）による強度低下を抑制する観点から、低粘度の液状物が好ましい。具体的には、２０℃における粘度が２５０ｍＰａ・ｓ以下の液状物が好ましい。本発明に係るグリセリン系粉砕助剤は、取扱いを容易にし、水硬性粉体の風化による水硬性組成物の硬化後の強度低下を抑制する観点から、グリセリンの水溶液が好ましく、グリセリン水溶液におけるグリセリンの濃度は５０〜９０重量％以下が好ましい。 The glycerin-based grinding aid according to the present invention is preferably a low-viscosity liquid material from the viewpoints of handleability and suppression of strength reduction due to weathering of the hydraulic powder (reaction with water in the air or carbonation). Specifically, a liquid material having a viscosity at 20 ° C. of 250 mPa · s or less is preferable. The glycerin-based grinding aid according to the present invention is preferably an aqueous solution of glycerin from the viewpoint of facilitating handling and suppressing a decrease in strength after curing of the hydraulic composition due to weathering of the hydraulic powder. The concentration is preferably 50 to 90% by weight or less.
本発明では、原料、用途等により、適当な粒径の粉体が得られるよう、粉砕の条件を調整すればよい。一般に、比表面積、ブレーン値が好ましくは２５００〜５０００ｃｍ2／ｇ、より好ましくは２８００〜４６００ｃｍ2／ｇの粉体となるまで、水硬性化合物、なかでもクリンカーの粉砕を行うことが好ましい。 In the present invention, the pulverization conditions may be adjusted so that a powder having an appropriate particle diameter can be obtained depending on the raw material, application, and the like. In general, it is preferable to grind the hydraulic compound, especially clinker, until the specific surface area and the brain value are preferably 2500 to 5000 cm 2 / g, more preferably 2800 to 4600 cm 2 / g.
本発明において、水硬性化合物、なかでもクリンカーの粉砕、なかでも仕上粉砕に使用される粉砕装置は、特に限定されないが、例えばセメントなどの粉砕で汎用されているボールミルを挙げることができる。該装置の粉砕媒体（粉砕ボール）の材質は、被粉砕物（例えばセメントクリンカーの場合、カルシウムアルミネート）と同等又はそれ以上の硬度を有するものが望ましく、一般に入用可能な市販品では、例えば鋼、アルミナ、ジルコニア、チタニア、タングステンカーバイド等を挙げることができる。 In the present invention, a pulverizing apparatus used for pulverization of a hydraulic compound, especially clinker, especially finish pulverization is not particularly limited, and examples thereof include a ball mill which is widely used for pulverization of cement and the like. The material of the grinding media (grinding balls) of the apparatus is preferably one having a hardness equal to or higher than that of the material to be ground (for example, calcium aluminate in the case of cement clinker). Examples thereof include steel, alumina, zirconia, titania, tungsten carbide and the like.
グリセリンと水及び／又は炭素数１〜４の１価アルコール化合物とを含む組成物、なかでもグリセリンと水とを含む組成物は、水硬性化合物、なかでもクリンカーに対する粉砕助剤として好適である。すなわち、水硬性化合物、なかでもクリンカーを粉砕、なかでも仕上げ粉砕する際に、粉砕助剤として、グリセリンと、水及び／又は炭素数１〜４の１価アルコールとを用いる水硬性化合物、なかでもクリンカーの粉砕方法が提供される。その場合、水硬性化合物１００重量部、なかでもクリンカー１００重量部に対して、グリセリンと、水及び／又は炭素数１〜４の１価アルコールの合計量で０．００１〜０．２重量部、さらに０．００５〜０．１重量部用い、グリセリンは０．００１〜０．２重量部、さらに０．０１〜０．１重量部用いることが好ましい。 A composition containing glycerin and water and / or a monohydric alcohol compound having 1 to 4 carbon atoms, particularly a composition containing glycerin and water, is suitable as a grinding compound for a hydraulic compound, particularly clinker. That is, a hydraulic compound, particularly a hydraulic compound using glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms as a grinding aid when grinding a clinker, especially finishing pulverization, A method for grinding clinker is provided. In that case, 0.001 to 0.2 parts by weight of the total amount of glycerin and water and / or monohydric alcohol having 1 to 4 carbon atoms with respect to 100 parts by weight of the hydraulic compound, in particular, 100 parts by weight of the clinker. Further, 0.005 to 0.1 part by weight is used, and glycerol is preferably used in an amount of 0.001 to 0.2 part by weight, and further 0.01 to 0.1 part by weight.
本発明に係るグリセリン系粉砕助剤は、グリセリンに加え、水と炭素数１〜４の１価アルコールを併用してもよく、また、炭素数１〜４の１価アルコールは２種以上を併用してもよい。さらに、その他の粉砕助剤を併用して使用することができる。例えば、その他の粉砕助剤は、粉砕助剤全体の好ましくは４０重量％以下、より好ましくは２０重量％以下、さらに好ましくは５重量％以下の量を配合して用いることができる。その他の粉砕助剤は、本発明に係るグリセリン系粉砕助剤より低粘度の化合物であることが取り扱い性の観点から好ましい。少量で低粘度化効果のあるジエチレングリコールやトリエタノールアミンを配合しても良い。 The glycerin-based grinding aid according to the present invention may use water and a monohydric alcohol having 1 to 4 carbon atoms in addition to glycerin, and the monohydric alcohol having 1 to 4 carbon atoms may be used in combination of two or more. May be. Furthermore, other grinding aids can be used in combination. For example, the other grinding aids can be used in an amount of preferably 40% by weight or less, more preferably 20% by weight or less, and still more preferably 5% by weight or less of the whole grinding aid. The other grinding aid is preferably a compound having a lower viscosity than the glycerin grinding aid according to the present invention from the viewpoint of handleability. You may mix | blend diethylene glycol and a triethanolamine with a low viscosity effect in a small quantity.
本発明に係るグリセリン系粉砕助剤を用いて得られる水硬性粉体としては、ポルトランドセメント、高炉スラグ、アルミナセメント、フライアッシュ、石灰石、石膏等が挙げられ、粉砕に供する水硬性化合物は、これら水硬性粉体の原料である。 Examples of the hydraulic powder obtained using the glycerin-based grinding aid according to the present invention include Portland cement, blast furnace slag, alumina cement, fly ash, limestone, gypsum, and the like. It is a raw material for hydraulic powder.
本発明では、グリセリンと、水及び／又は炭素数１〜４の１価アルコールとを含有する粉砕助剤の存在下で水硬性化合物を粉砕する水硬性粉体の製造方法が提供され、この方法では、粉砕助剤は、水硬性化合物への添加しやすさと水硬性組成物の初期強度発現の観点から、グリセリンと水及び／又は炭素数１〜４の１価アルコールとを、グリセリン／（水及び／又は炭素数１〜４の１価アルコール）が９０／１０〜５０／５０の重量比で含有するものが好ましい。また、この方法では、粉砕助剤は、グリセリンと水及び／又は炭素数１〜４の１価アルコールとの合計の存在量が、水硬性化合物１００重量部に対して、０．００１〜０．２重量部であることが好ましい。 In this invention, the manufacturing method of the hydraulic powder which grind | pulverizes a hydraulic compound in presence of the grinding | pulverization adjuvant containing glycerol and water and / or a C1-C4 monohydric alcohol is provided, and this method Then, from the viewpoint of ease of addition to the hydraulic compound and expression of the initial strength of the hydraulic composition, the pulverization aid is obtained by combining glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms with glycerin / (water. And / or monohydric alcohol having 1 to 4 carbon atoms) is preferably contained in a weight ratio of 90/10 to 50/50. Further, in this method, the grinding aid has a total abundance of glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms with respect to 100 parts by weight of the hydraulic compound. 2 parts by weight is preferred.
本発明では、下記の一般式（１）で表される単量体（以下、単量体１という）由来の構成単位１と下記の一般式（２）で表される単量体（以下、単量体２という）由来の構成単位２とを有する重合体（以下、重合体Ａという）が用いられる。 In the present invention, a structural unit 1 derived from a monomer represented by the following general formula (1) (hereinafter referred to as monomer 1) and a monomer represented by the following general formula (2) (hereinafter, A polymer having a structural unit 2 derived from (referred to as monomer 2) (hereinafter referred to as polymer A) is used.
〔式中、Ｒ1、Ｒ2は、それぞれ水素原子又はメチル基、Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4、ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基、ｐは０又は１の数、ｑは０〜２の数、ｒはＡＯの平均付加モル数であり、３〜３００の数、Ｒ4は水素原子又は炭素数１〜１８のアルキル基を表す。〕 [In the formula, R 1 and R 2 are each a hydrogen atom or a methyl group, R 3 is a hydrogen atom, or — (CH 2 ) q (CO) p O (AO) r R 4 , and AO has 2 to 4 carbon atoms. Oxyalkylene group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R 4 is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]
〔式中、Ｒ5〜Ｒ7は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよく、その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の数を表す。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属（1/2原子）、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基を表す。〕 Wherein, R 5 to R 7 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or another (CH 2) s COOM 2 and anhydrous In this case, M 1 and M 2 of those groups are not present. s represents the number of 0-2. M 1 and M 2 each represent a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
［単量体１］
単量体１において、一般式（１）中のＲ1、Ｒ2は、それぞれ水素原子又はメチル基である。Ｒ3は水素原子又は-(ＣＨ2)q(ＣＯ)pＯ(ＡＯ)rＲ4であり、水素原子が好ましい。一般式（１）のアルケニル〔(Ｒ1)(Ｒ3)Ｃ＝Ｃ(Ｒ2)−(ＣＨ2)q−〕として、ビニル基、アリル基、メタリル基等が挙げられる。ｐが０の場合はＡＯは(ＣＨ2)qとエーテル結合、ｐが１の場合はエステル結合をする。ｑは０〜２であり、好ましくは０又は１であり、さらに好ましくは０である。ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基であり、ＡＯは炭素数２〜４のオキシアルキレン基が好ましく、エチレンオキシ基を含むことがより好ましく、ＥＯ基が７０モル％以上、さらに８０モル％以上、さらに９０モル％以上、よりさらに全ＡＯがＥＯ基であることが好ましい。ｒはＡＯの平均付加モル数であり、３〜３００の数であり、水硬性組成物の初期強度発現の観点から、好ましくは５０〜３００、より好ましくは１１０〜３００である。また、平均ｒ個の繰り返し単位中にＡＯが異なるもので、ランダム付加又はブロック付加又はこれらの混在を含むものであっても良い。例えばＡＯは、ＥＯ基以外にもプロピレンオキシ基等を含むこともできる。単量体１は、ｐ＝１でｑ＝０の化合物が好ましい。また、ｐ＝０のとき、ｑ＝１が好ましい。
[Monomer 1]
In monomer 1, R 1 and R 2 in general formula (1) are each a hydrogen atom or a methyl group. R 3 is a hydrogen atom or — (CH 2 ) q (CO) p O (AO) r R 4 , preferably a hydrogen atom. Examples of the alkenyl [(R 1 ) (R 3 ) C═C (R 2 ) — (CH 2 ) q —] in the general formula (1) include a vinyl group, an allyl group, and a methallyl group. When p is 0, AO forms an ether bond with (CH 2 ) q, and when p is 1, it forms an ester bond. q is 0 to 2, preferably 0 or 1, and more preferably 0. AO is an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group, and an EO group of 70 mol% or more, Furthermore, it is preferable that 80 mol% or more, further 90 mol% or more, and further all AO is an EO group. r is the average added mole number of AO, is a number of 3 to 300, and is preferably 50 to 300, more preferably 110 to 300, from the viewpoint of expression of the initial strength of the hydraulic composition. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. For example, AO can contain a propyleneoxy group etc. besides EO group. Monomer 1 is preferably a compound with p = 1 and q = 0. Further, when p = 0, q = 1 is preferable.
重合体Ａは、水硬性組成物の初期強度と流動性を高いレベルで実現するために、単量体１の一般式（１）中のｒは５０〜３００が好ましく、１１０〜３００がより好ましい。重合性からｒは好ましくは２００以下、より好ましくは１５０以下、さらに好ましくは１３０以下である。したがって、総合的な観点から、ｒは５０〜２００が好ましく、１１０〜１５０がより好ましく、１１０〜１３０がさらに好ましい。 In the polymer A, in order to realize the initial strength and fluidity of the hydraulic composition at a high level, r in the general formula (1) of the monomer 1 is preferably 50 to 300, and more preferably 110 to 300. . In view of polymerizability, r is preferably 200 or less, more preferably 150 or less, and still more preferably 130 or less. Therefore, from a comprehensive viewpoint, r is preferably 50 to 200, more preferably 110 to 150, and still more preferably 110 to 130.
Ｒ4は水素原子又は炭素数１〜１８のアルキル基であり、さらに１〜１２、さらに１〜４、さらに１、２のアルキル基が好ましく、中でもメチル基が好ましい。 R 4 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 4, and further preferably 1 or 2, and particularly preferably a methyl group.
単量体１としては、メトキシポリエチレングリコール、メトキシポリプロピレングリコール、メトキシポリブチレングリコール、メトキシポリスチレングリコール、エトキシポリエチレンポリプロピレングリコール等の片末端アルキル封鎖ポリアルキレングリコールと（メタ）アクリル酸、マレイン酸との（ハーフ）エステル化物や、（メタ）アリルアルコールとのエーテル化物、及び（メタ）アクリル酸、マレイン酸、（メタ）アリルアルコールへの炭素数２〜４のアルキレンオキシド付加物付加物が好ましく用いられる。 Monomer 1 includes a half-terminated alkyl-capped polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, (meth) acrylic acid, maleic acid (half ) Esterified products, etherified products with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, and (meth) allyl alcohol adducts having 2 to 4 carbon atoms are preferably used.
より好ましくはアルコキシ、中でもメトキシポリエチレングリコールと（メタ）アクリル酸とのエステル化物である。具体的には、ω−メトキシポリオキシアルキレンメタクリル酸エステル、ω−メトキシポリオキシアルキレンアクリル酸エステル等を挙げることができ、ω−メトキシポリオキシアルキレンメタクリル酸エステルがより好ましい。 More preferred is an esterified product of alkoxy, especially methoxypolyethylene glycol and (meth) acrylic acid. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable.
重合体Ａが、ｒの異なる複数の単量体１を用いて得られる場合は、ｒは重合体全体の平均値を表す。例えば、重合体Ａがｒ＝ｒ1である単量体をｘ1モル％、ｒ＝ｒ2である単量体をｘ2モル％用いて得られる場合、ｒは、ｒ＝（ｒ1ｘ1＋ｒ2ｘ2）／（ｘ1＋ｘ2）
により求められる。
When the polymer A is obtained using a plurality of monomers 1 having different r, r represents an average value of the whole polymer. For example, when the polymer A is obtained using x 1 mol% of a monomer where r = r 1 and x 2 mol% of a monomer where r = r 2 , r is r = (r 1 x 1 + r 2 x 2 ) / (x 1 + x 2 )
Is required.
［単量体２］
単量体２において、一般式（２）中のＲ5〜Ｒ7は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよい。その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の数を表す。Ｒ5は水素原子が好ましく、Ｒ6はメチル基が好ましい。Ｒ7は水素原子又は(ＣＨ2)sＣＯＯＭ2が好ましい。
[Monomer 2]
In the monomer 2, R 5 to R 7 in the general formula (2) are each a hydrogen atom, a methyl group, or (CH 2 ) s COOM 2 , and (CH 2 ) s COOM 2 is COOM 1 or other (CH 2 ) s COOM 2 and an anhydride may be formed. In that case, M 1 and M 2 of those groups do not exist. s represents the number of 0-2. R 5 is preferably a hydrogen atom, and R 6 is preferably a methyl group. R 7 is preferably a hydrogen atom or (CH 2 ) s COOM 2 .
Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属（1/2原子）、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基である。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属が好ましい。 M 1 and M 2 are each a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. M 1 and M 2 are each preferably a hydrogen atom or an alkali metal.
具体的には、（メタ）アクリル酸、クロトン酸等のモノカルボン酸系単量体、マレイン酸、イタコン酸、フマル酸等のジカルボン酸系単量体、又はこれらの無水物もしくは塩（例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、水酸基が置換されていてもよいモノ、ジ、トリアルキル（炭素数２〜８）アンモニウム塩）もしくはエステルが挙げられ、好ましくは（メタ）アクリル酸、マレイン酸、無水マレイン酸、さらに好ましくは（メタ）アクリル酸又はこれらのアルカリ金属塩である。なお、（メタ）アクリル酸は、アクリル酸及び／又はメタクリル酸の意味である（以下同様）。 Specifically, monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid, or anhydrides or salts thereof (for example, alkalis) Metal salt, alkaline earth metal salt, ammonium salt, mono-, di-, trialkyl (carbon number 2 to 8) ammonium salt optionally substituted with hydroxyl group) or ester, preferably (meth) acrylic acid, Maleic acid, maleic anhydride, more preferably (meth) acrylic acid or an alkali metal salt thereof. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid (hereinafter the same).
重合体Ａは、例えば反応容器に水を仕込み昇温し、その中で単量体１と単量体２とを連鎖移動剤等の存在下、モル比及び重量比を一定として反応させ、熟成することにより製造することができる。必要により熟成後中和する。 Polymer A is prepared by, for example, charging water in a reaction vessel and raising the temperature, and reacting monomer 1 and monomer 2 in the presence of a chain transfer agent or the like at a constant molar ratio and weight ratio, and aging. Can be manufactured. Neutralize after aging if necessary.
重合体Ａの製造に用いる単量体１と単量体２の重量比（単量体１／単量体２）は９７／３〜３／９７が好ましく、９５／５〜５０／５０がより好ましく、９０／１０〜７０／３０がさらに好ましい。 The weight ratio (monomer 1 / monomer 2) of monomer 1 and monomer 2 used for production of polymer A is preferably 97/3 to 3/97, more preferably 95/5 to 50/50. 90/10 to 70/30 is more preferable.
重合体Ａにおいて、該重合体を製造するために用いられる単量体２の全単量体に対する平均重量比(YI)が５〜５０（重量％）、さらに１０〜３０（重量％）であることが好ましい。平均重量比は、〔単量体２の合計量／重合体Ａ’の合成に用いた全単量体の合計量〕×100（重量％）で表される。重合体Ａの汎用性をより広くするには、該重合体Ａの平均重量比とは異なる平均重量比(YII)により製造された重合体Ａ’を併用することが好ましい。 In the polymer A, the average weight ratio (Y I ) of the monomer 2 used for producing the polymer to all monomers is 5 to 50 (wt%), and further 10 to 30 (wt%). Preferably there is. The average weight ratio is represented by [total amount of monomer 2 / total amount of all monomers used for the synthesis of polymer A ′] × 100 (% by weight). In order to broaden the versatility of the polymer A, it is preferable to use a polymer A ′ produced with an average weight ratio (Y II ) different from the average weight ratio of the polymer A in combination.
重合体Ａ及びＡ’は、平均重量比(YI)と(YII)とが２以上異なるように選択することが好ましい。なお、重合体Ａ及びＡ’とで、製造に用いる単量体１及び２の種類が異なっていても同一であってもよいが、同一の種類のものを用いることが好ましい。 The polymers A and A ′ are preferably selected so that the average weight ratio (Y I ) and (Y II ) are different by 2 or more. The polymers A and A ′ may be the same or different in the types of monomers 1 and 2 used in the production, but it is preferable to use the same type.
また、本発明では、重合体Ａとして、単量体１の少なくとも１種と単量体２の少なくとも１種とを共重合させて得られ、且つ前記単量体１と単量体２のモル比［単量体１］／［単量体２］が反応途中において少なくとも１回変化されている共重合体混合物〔以下、共重合体混合物(A)ともいう〕を用いることもできる。このような共重合体混合物(A)は、反応系に添加する単量体１と単量体２のモル比［単量体１］／［単量体２］を反応途中において少なくとも１回変化することにより製造することができる。その際、モル比［単量体１］／［単量体２］の最大値と最小値の差が少なくとも0.05以上、さらに0.05〜2.5の範囲にあることが好ましい。 Further, in the present invention, the polymer A is obtained by copolymerizing at least one monomer 1 and at least one monomer 2 and is a mole of the monomer 1 and the monomer 2. It is also possible to use a copolymer mixture in which the ratio [monomer 1] / [monomer 2] is changed at least once during the reaction [hereinafter also referred to as copolymer mixture (A)]. Such a copolymer mixture (A) changes the molar ratio [monomer 1] / [monomer 2] of monomer 1 and monomer 2 added to the reaction system at least once during the reaction. Can be manufactured. In that case, it is preferable that the difference between the maximum value and the minimum value of the molar ratio [monomer 1] / [monomer 2] is at least 0.05 or more, and more preferably in the range of 0.05 to 2.5.
共重合体混合物(A)は、上記単量体１及び２とを、好ましくは［単量体１］／［単量体２］＝0.02〜４の範囲のモル比で反応させて得られるが、これらのモル比［単量体１］／［単量体２］は反応途中において少なくとも１回変化されることが好ましい。そして、本発明では、共重合体混合物(A)を製造するための全単量体に対する単量体２の平均重量比(YI)と異なる平均重量比(YII)により得られた共重合体混合物(A')を併用することが好ましい。すなわち、共重合体混合物(A')は、上記単量体１及び２とを、好ましくは［単量体１］／［単量体２］＝0.02〜４の範囲のモル比で反応させて得られた共重合体混合物であって、これらのモル比［単量体１］／［単量体２］は反応途中において少なくとも１回変化されており、該共重合体混合物(A')を製造するための全単量体に対する単量体(A2)の平均重量比(YII)が、共重合体混合物(A)における平均重量比(YI)とは異なるものである。平均重量比は、〔単量体(A2)の合計量／全単量体量〕×100（重量％）で表され、それぞれ１０〜５０（重量％）の範囲にあることが好ましい。なお、以下この平均重量比を「(A2)’平均重量比」という場合もある。また、この平均重量比(YI)、(YII)の差は、好ましくは0.1（重量％）以上、より好ましくは0.5（重量％）以上、さらに好ましくは1.0（重量％）以上相違することが好ましい。なお、共重合体混合物(A)と(A')とで、製造に用いる単量体１及び２の種類が異なっていても、本発明では平均重量比(YI)、(YII)が異なっていればよいが、単量体１及び２として同一の種類のものを用いるのが好ましい。 The copolymer mixture (A) is obtained by reacting the above monomers 1 and 2 with a molar ratio of preferably [monomer 1] / [monomer 2] = 0.02-4. The molar ratio [monomer 1] / [monomer 2] is preferably changed at least once during the reaction. In the present invention, the copolymer weight obtained with an average weight ratio (Y II ) different from the average weight ratio (Y I ) of the monomer 2 to the total monomers for producing the copolymer mixture (A). It is preferable to use the coalescence mixture (A ′) in combination. That is, the copolymer mixture (A ′) is prepared by reacting the monomers 1 and 2 with a molar ratio preferably in the range of [Monomer 1] / [Monomer 2] = 0.02-4. In the obtained copolymer mixture, the molar ratio [monomer 1] / [monomer 2] was changed at least once during the reaction, and the copolymer mixture (A ′) The average weight ratio (Y II ) of the monomer (A2) to the total monomers for production is different from the average weight ratio (Y I ) in the copolymer mixture (A). The average weight ratio is represented by [total amount of monomers (A2) / total amount of monomers] × 100 (% by weight), and is preferably in the range of 10 to 50 (% by weight). Hereinafter, this average weight ratio may be referred to as “(A2) ′ average weight ratio”. The difference between the average weight ratios (Y I ) and (Y II ) is preferably 0.1 (wt%) or more, more preferably 0.5 (wt%) or more, and even more preferably 1.0 (wt%) or more. Is preferred. Even if the copolymer mixtures (A) and (A ′) are different in the types of monomers 1 and 2 used in the production, the average weight ratios (Y I ) and (Y II ) are As long as they are different, it is preferable to use the same kind of monomers 1 and 2.
また、本発明では、重合体Ａに用いる単量体２として一般式（２）中のＭ1、Ｍ2がアルキル基（好ましくは炭素数１〜３）、ヒドロキシアルキル基（好ましくは炭素数２〜５）、又はアルケニル基（好ましくは炭素数２〜５）である化合物を用いた重合体（以下、重合体Ａ''という）を用いることができる。 In the present invention, as monomer 2 used for polymer A, M 1 and M 2 in general formula (2) are alkyl groups (preferably having 1 to 3 carbon atoms) and hydroxyalkyl groups (preferably having 2 carbon atoms). To 5), or a polymer using a compound having an alkenyl group (preferably having 2 to 5 carbon atoms) (hereinafter referred to as polymer A ″) can be used.
この場合、重合体Ａ''の製造に用いる単量体１の好ましい構造、種類は前記したものと同じである。 In this case, the preferable structure and type of the monomer 1 used for the production of the polymer A ″ are the same as those described above.
重合体Ａの製造においては、上記単量体１及び２の他に、１種以上の共重合可能なその他の単量体を用いることもできる。共重合可能な他の単量体としては、アリルスルホン酸、メタリルスルホン酸、スルホエチルメタクリレートこれら何れかのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、又はアミン塩。（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、２−（メタ）アクリルアミド−２−メタスルホン酸、２−（メタ）アクリルアミド−２−エタンスルホン酸、２−（メタ）アクリルアミド−２−プロパンスルホン酸、スチレン、スチレンスルホン酸などが挙げられる。さらに、特許第３３３６４５６号公報に記載の如くポリアルキレンポリアミンと二塩基酸または二塩基酸と炭素原子数１ないし４の低級アルコールとのエステルと、アクリル酸もしくはメタクリル酸またはアクリル酸もしくはメタクリル酸と炭素原子数１ないし４の低級アルコールとのエステルを縮合させて得られたポリアマイドポリアミンのアミノ残基に対して炭素原子数２ないし４のアルキレンオキサイドを付加して成るポリアマイドポリアミン系単量体、特開２００４−２１７４号公報に記載の如くポリアルキレンポリアミンと二塩基酸及び／又は二塩基酸と炭素数１〜４のアルコールとのエステル、並びに(メタ)アクリル酸及び／又は(メタ)アクリル酸と炭素数１〜４のアルコールとのエステルを反応させて得られる不飽和結合を有するポリアミドポリアミンのアミノ残基及びイミノ基に対して炭素数２〜４のアルキレンオキシドを付加して成るポリアミドポリアミン系単量体、特開２００３−３３５５６３号公報に記載の如くアミンアルキレンオキシド付加物単量体、特開２００４−３４２０５０号公報に記載の如くポリアルキレンイミンアルキレンオキシド付加物単量体、特開２００４−６７９３４号公報に記載の如くポリ（ポリオキシアルキレン）系不飽和単量体等が挙げられる。単量体１及び２の合計の割合は、全単量体中３０〜１００モル％が好ましく、５０〜１００モル％がより好ましく、７５〜１００モル％がより好ましく、９０〜１００モル％がより好ましい。 In the production of the polymer A, in addition to the monomers 1 and 2, one or more other copolymerizable monomers can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, sulfoethyl methacrylate, alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts of any of these. (Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, 2- (Meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. Furthermore, as described in Japanese Patent No. 3336456, polyalkylene polyamine and dibasic acid or ester of dibasic acid and lower alcohol having 1 to 4 carbon atoms, acrylic acid or methacrylic acid or acrylic acid or methacrylic acid and carbon A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amino residue of a polyamide polyamine obtained by condensing an ester with a lower alcohol having 1 to 4 atoms; As described in JP-A-2004-2174, an ester of a polyalkylene polyamine and a dibasic acid and / or a dibasic acid and an alcohol having 1 to 4 carbon atoms, and (meth) acrylic acid and / or (meth) acrylic acid Having an unsaturated bond obtained by reacting an ester with an alcohol having 1 to 4 carbon atoms A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the amino residue and imino group of a polyamide polyamine, an amine alkylene oxide adduct as described in JP-A-2003-335563. A polyalkyleneimine alkylene oxide adduct monomer as described in JP-A No. 2004-342050, a poly (polyoxyalkylene) unsaturated monomer as described in JP-A No. 2004-67934, and the like. Can be mentioned. The total ratio of the monomers 1 and 2 is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and more preferably 90 to 100 mol% in all monomers. preferable.
重合体Ａは市販品を用いることもでき、具体的には以下のものが例示される。これらを二種以上併用しても良い。 The polymer A can also use a commercial item, and specifically, the following are illustrated. Two or more of these may be used in combination.
花王（株）製のマイテイ3000S、マイテイ3000H、マイテイ3000R、マイテイ21LV、マイテイ21VS、マイテイ21HF、マイテイ21HP、（株）日本触媒製のアクアロックFC600S、FC900アクアロック、日本油脂（株）製のマリアリムAKM-60F、マリアリムEKM-60K、マリアリムY-40、Degussa社製のレオビルドSPシリーズ（8LS,8LSR,8N,8S,8R, 8SE, 8RE, 8SB-S, 8SB-M, 8SB-L, 8SB-LL, 8HE, 8HR, 8SV, 8RV）、レオビルド8000S、8000E, 8000H、Glenium series (3030NS, 3400NV, 3000NS, 3200HES, 27, 51, 206, C301, C323, C315, ACE28,ACE30, ACE32, ACE38, ACE40, ACE48, ACE68, ACE327, ACE329, ACE338, SKY501, SKY503, SKY505, SKY528, SKY591, SKY592, SKY593, SKY910+, SP-8CR, SP-8CN, SP-8N, 8000,SP-8L)、Melflux1641, 2453, 2424,2500、Sika社製のシーカメント1200N,1100NT,1100NTR,1100NT-PWR,1100NT-PSK,2300、Sikament686, Sika Viscocrete2100, Sika Viscocrete4100, Sika Viscocrete6100, Sika Viscocrete 20HE, Sikament 5370, Sika Viscocrete3010, Sika Viscocrete5-500, Sika Viscocrete5-300, Sika Viscocrete5, Sika Viscocrete20SL、竹本油脂（株）製のチューポールHP-8、チューポールHP-11、チューポールHP-8R、チューポールHP-11R、チューポールHP-11X、チューポールSSP-104、チューポールSSP-116、チューポールHP70、チューポールNV-G1、チューポールNV-G5、（株）フローリック製のフローリックSF500S、フローリックSF500SB、フローリックSF500H、フローリックSF500R、フローリックSF500RB、GRACE社製のADVA CAST 570, ADVA Flow 340, ADVA Flow 341, ADVA Flow 355, ADVA Flow 356, ADVA Flow 400、ADVA 100 Superplasticizer, ADVA 140, ADVA 170, ADVA 360, ADVA 370, ADVA Cast 500, ADVA Cast 530, ADVA Cast 540, ADVA Cast 555、BASF社製のSokalan series (HP80, 5009X, 5010X, DS3557, R401)、Kyunggi社製のPowerflow series (WR, HWR, SR)、Mapei社製のDynamon series, Mapeifluid series (Mapei)、Fosroc社製のStrucuro series等が挙げられる。 Mighty 3000S, Mighty 3000H, Mighty 3000R, Mighty 21LV, Mighty 21VS, Mighty 21HF, Mighty 21HP manufactured by Kao Corporation, Aqualock FC600S, FC900 Aqualock manufactured by Nippon Shokubai Co., Ltd. AKM-60F, Mariarim EKM-60K, Mariarim Y-40, Degussa's Leo Build SP Series (8LS, 8LSR, 8N, 8S, 8R, 8SE, 8RE, 8SB-S, 8SB-M, 8SB-L, 8SB- LL, 8HE, 8HR, 8SV, 8RV), Leobuild 8000S, 8000E, 8000H, Glenium series (3030NS, 3400NV, 3000NS, 3200HES, 27, 51, 206, C301, C323, C315, ACE28, ACE30, ACE32, ACE38, ACE40 , ACE48, ACE68, ACE327, ACE329, ACE338, SKY501, SKY503, SKY505, SKY528, SKY591, SKY592, SKY593, SKY910 +, SP-8CR, SP-8CN, SP-8N, 8000, SP-8L), Melflux1641, 2453, 2424,2500, Sika's Sikament 1200N, 1100NT, 1100NTR, 1100NT-PWR, 1100NT-PSK, 2300, Sikament686, Sika Viscocrete2100, Sika Viscocrete4100, Sika Viscocrete6100, Sika Viscocrete 20HE, Sika Viscocrete3 010, Sika Viscocrete5-500, Sika Viscocrete5-300, Sika Viscocrete5, Sika Viscocrete20SL, Tupole HP-8, Tupole HP-11, Tupole HP-8R, Tupole HP-11R, Chupol Paul HP-11X, Tupole SSP-104, Tupole SSP-116, Tupole HP70, Tupole NV-G1, Tupole NV-G5, Floric SF500S, Floric SF500SB, Floric SF500H, Floric SF500R, Floric SF500RB, manufactured by GRACE ADVA CAST 570, ADVA Flow 340, ADVA Flow 341, ADVA Flow 355, ADVA Flow 356, ADVA Flow 400, ADVA 100 Superplasticizer, ADVA 140, ADVA 170, ADVA 360 , ADVA 370, ADVA Cast 500, ADVA Cast 530, ADVA Cast 540, ADVA Cast 555, Sokalan series (HP80, 5009X, 5010X, DS3557, R401) from BASF, Powerflow series (WR, HWR, SR from Kyunggi) ), Mapei Dynamon series, Mapeifluid series (Mapei), Fosroc Strucuro series, etc. It is.
本発明では、上記本発明に係るグリセリン系粉砕助剤の存在下で水硬性化合物を粉砕して得られる水硬性粉体と、上記重合体Ａと、水を混合して、前記水硬性粉体と前記重合体とを含有する水硬性組成物を製造する。重合体Ａは、水硬性粉体１００重量部に対して、０．００５〜０．５重量部用いることが好ましく、０．０１〜０．３重量部がより好ましく、０．０５〜０．２５重量部がさらに好ましい。水は後述する水／水硬性粉体比となるように用いることが好ましい。これらの混合は、通常の水硬性組成物の製造に用いられる装置、条件等を採用して行うことができる。 In the present invention, the hydraulic powder obtained by mixing a hydraulic powder obtained by pulverizing a hydraulic compound in the presence of the glycerin-based pulverization aid according to the present invention, the polymer A, and water is mixed. And a hydraulic composition containing the polymer. The polymer A is preferably used in an amount of 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, and 0.05 to 0.25 based on 100 parts by weight of the hydraulic powder. Part by weight is more preferred. Water is preferably used so as to have a water / hydraulic powder ratio described later. These mixings can be carried out by employing equipment, conditions and the like used in the production of ordinary hydraulic compositions.
水硬性粉体に、水、化学混和剤、砂等の細骨材及び砂利等の粗骨材の骨材が添加されて最終的に得られる水硬性組成物が、一般にそれぞれモルタル、コンクリートなどと呼ばれている。本発明はこのような水硬性組成物の製造に用いられ、具体的には、生コンクリート、コンクリート振動製品用、セルフレベリング用、耐火物用、プラスター用、石膏スラリー用、軽量又は重量コンクリート用、ＡＥ用、補修用、プレパックド用、トレーミー用、グラウト用、地盤改良用、寒中用等の種々の分野に用いられる水硬性組成物が対象となる。 The hydraulic composition finally obtained by adding water, chemical admixture, fine aggregate such as sand and coarse aggregate such as gravel to the hydraulic powder is generally obtained as mortar, concrete, etc., respectively. being called. The present invention is used for the production of such a hydraulic composition, specifically, ready-mixed concrete, for concrete vibration products, for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, The hydraulic compositions used in various fields such as AE, repair, prepacked, trayy, grout, ground improvement, and cold use are targeted.
本発明により製造された水硬性組成物は、水／水硬性粉体比（Ｗ／Ｐ）は、６５重量％以下、さらに１０〜６０重量％、さらに１２〜５７重量％、さらに１５〜５５重量％、よりさらに２０〜５５重量％であることが好ましい。Ｗ／Ｐは、水硬性組成物中の水（Ｗ）と水硬性粉体（Ｐ）の重量百分率（重量％）、すなわち、（Ｗ／Ｐ）×１００で算出されるものである。なお、水硬性粉体は、セメント等の水硬性無機粉末が代表例であるが、水硬性組成物の調製に用いた無機粉末のうち、水硬性粉末に該当する粉末、例えば、シリカフューム、高炉スラグ、フライアッシュ、石灰石微粉末等の混和材料も、それらの重量をＰの重量に算入するものとする。なお、水硬性粉体とは、水と反応して硬化する性質をもつ粉体、及び単一物質では硬化性を有しないが、２種以上を組み合わせると水を介して相互作用により水和物を形成し硬化する粉体のことである。 The hydraulic composition produced according to the present invention has a water / hydraulic powder ratio (W / P) of 65% by weight or less, further 10 to 60% by weight, further 12 to 57% by weight, and further 15 to 55% by weight. %, More preferably 20 to 55% by weight. W / P is calculated by weight percentage (% by weight) of water (W) and hydraulic powder (P) in the hydraulic composition, that is, (W / P) × 100. The hydraulic powder is typically a hydraulic inorganic powder such as cement, but among the inorganic powders used for preparing the hydraulic composition, the powder corresponding to the hydraulic powder, such as silica fume, blast furnace slag, etc. In addition, admixtures such as fly ash and fine powder of limestone are also included in the weight of P. The hydraulic powder is a powder having a property of curing by reacting with water, and a single substance does not have curability, but when two or more kinds are combined, a hydrate is obtained by interaction through water. It is a powder that forms and hardens.
さらに、本発明により製造された水硬性組成物は、初期強度が高いために、型枠にコンクリートが付着することなく容易に脱型することが可能となり、表面美観の改善に効果がある。例えば、本発明により製造された水硬性組成物は、該水硬性組成物を型枠に充填し成形した後、適宜養生した後、脱型を行うコンクリート製品の製造方法に供することができる。その際、型枠内に水硬性組成物を十分に充填する観点から型枠に充填後、振動機による締め固めを行うことが好ましい。この方法に使用される水硬性組成物（生コンクリート）の流動性は、スランプ値（ＪＩＳ Ａ １１０１）は１ｃｍ〜２３ｃｍ、スランプフロー値（ＪＩＳ Ａ １１５０）は３０ｃｍ〜７５ｃｍであることが好ましい。モルタルフロー値では１５０〜３００ｍｍであることが好ましい。 Furthermore, since the hydraulic composition produced by the present invention has high initial strength, it can be easily demolded without adhering concrete to the mold, which is effective in improving the surface appearance. For example, the hydraulic composition produced according to the present invention can be used in a method for producing a concrete product in which the hydraulic composition is filled into a mold and molded, and then appropriately cured, followed by demolding. At that time, from the viewpoint of sufficiently filling the mold with the hydraulic composition, it is preferable to perform compaction with a vibrator after filling the mold. As for the fluidity of the hydraulic composition (green concrete) used in this method, the slump value (JIS A 1101) is preferably 1 cm to 23 cm, and the slump flow value (JIS A 1150) is preferably 30 cm to 75 cm. The mortar flow value is preferably 150 to 300 mm.
〔製造例Ａ−１〕（重合体Ａ−１の製造）
攪拌機付きガラス製反応容器（四つ口フラスコ）に水１１４ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。６０重量％のω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数１２０：エステル純度１００％）水溶液３００ｇ、メタクリル酸（試薬：和光純薬工業（株））１１．５ｇ、及びメルカプトプロピオン酸０．９８ｇを混合溶解した溶液と、過硫酸アンモニウム１．９ｇを水４５ｇに溶解した溶液の２者を、それぞれ１．５時間かけて上記反応容器中に滴下した。その後、１時間熟成し、さらに過硫酸アンモニウム０．８ｇを水１５ｇに溶解した溶液を３０分かけて滴下し、引き続き１．５時間熟成した。この一連の間の反応系の温度は８０℃に保たれた。熟成終了後に４０℃以下に冷却した後、４８重量％水酸化ナトリウム溶液９．６ｇで中和し、重量平均分子量５４０００の重合体Ａ−１を得た。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-1] (Production of Polymer A-1)
Into a glass reaction vessel (four-necked flask) equipped with a stirrer, 114 g of water was charged, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 60% by weight of ω-methoxypolyethylene glycol monomethacrylate (average addition mole number of ethylene oxide 120: ester purity 100%) aqueous solution 300 g, methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.) 11.5 g, and mercaptopropionic acid 0 Two solutions, a solution in which .98 g was mixed and dissolved, and a solution in which 1.9 g of ammonium persulfate was dissolved in 45 g of water were dropped into the reaction vessel over 1.5 hours. Thereafter, aging was performed for 1 hour, and a solution obtained by dissolving 0.8 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 9.6 g of a 48 wt% sodium hydroxide solution to obtain a polymer A-1 having a weight average molecular weight of 54,000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.
〔製造例Ａ−２〕（重合体Ａ−２の製造）
攪拌機付きガラス製反応容器（四つ口フラスコ）に水６８７ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数９：新中村化学製ＮＫエステルＭ９０Ｇ）８７．４ｇ、６０重量％のω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数１２０：エステル純度９７％）水溶液１０５２ｇ、メタクリル酸（試薬：和光純薬工業（株））２５．３ｇ、及びメルカプトプロピオン酸１．５ｇを混合溶解した溶液と、過硫酸アンモニウム１．３４ｇを水１２ｇに溶解した溶液の２者を、それぞれ１．５時間かけて上記反応容器中に滴下した。その後、１時間熟成し、さらに過硫酸アンモニウム０．７ｇを水６ｇに溶解した溶液を３０分かけて滴下し、引き続き１．５時間熟成した。この一連の間の反応系の温度は８０℃に保たれた。熟成終了後に４０℃以下に冷却した後、４８重量％水酸化ナトリウム溶液１４．４ｇで中和し、重量平均分子量５３０００の重合体Ａ−２を得た。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-2] (Production of Polymer A-2)
Into a glass reaction vessel (four-necked flask) equipped with a stirrer, 687 g of water was charged, and purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethylene glycol monomethacrylate (average addition mole number of ethylene oxide 9: NK ester M90G made by Shin-Nakamura Chemical Co., Ltd.) 87.4 g, 60 wt% ω-methoxypolyethylene glycol monomethacrylate (average addition mole number of ethylene oxide 120: ester purity 97%) of a solution in which 1052 g of an aqueous solution, 25.3 g of methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.) and 1.5 g of mercaptopropionic acid were mixed and dissolved, and a solution in which 1.34 g of ammonium persulfate was dissolved in 12 g of water. Two persons were dripped in the said reaction container over 1.5 hours, respectively. Thereafter, aging was performed for 1 hour, and a solution obtained by dissolving 0.7 g of ammonium persulfate in 6 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 14.4 g of a 48 wt% sodium hydroxide solution to obtain a polymer A-2 having a weight average molecular weight of 53,000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.
〔製造例Ａ−３〕（重合体Ａ−３の製造）
撹拌機付きガラス製反応容器（四つ口フラスコ）に水1053.1g仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で78℃まで昇温した。ω-メトキシポリエチレングリコールメタクリレート（エチレンオキサイドの付加モル数120）884.5ｇとメタクリル酸28.1ｇ、アクリル酸メチル98.5ｇと2-メルカプトエタノール5.11gを水526.5gに溶解したものと過硫酸アンモニウム11.18ｇを水63.4gに溶解したものの二者をそれぞれ1.5時間かけて滴下した。引き続き、過硫酸アンモニウム3.73ｇを水21.1ｇに溶解したものを30分かけて滴下し、その後1時間同温度（78℃）で熟成した。熟成終了後に20重量％水酸化ナトリウム69.4ｇで中和し、重合体Ａ−３を得た（重量平均分子量81000）。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-3] (Production of Polymer A-3)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 1053.1 g of water, purged with nitrogen while stirring, and heated to 78 ° C. in a nitrogen atmosphere. 884.5 g of ω-methoxypolyethylene glycol methacrylate (additional mole number of ethylene oxide 120), 28.1 g of methacrylic acid, 98.5 g of methyl acrylate and 5.11 g of 2-mercaptoethanol dissolved in 526.5 g of water and 11.18 g of ammonium persulfate in water The two dissolved in 63.4 g were added dropwise over 1.5 hours. Subsequently, a solution obtained by dissolving 3.73 g of ammonium persulfate in 21.1 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (78 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 69.4 g of 20 wt% sodium hydroxide to obtain a polymer A-3 (weight average molecular weight 81000). Then, it adjusted to 20 weight% of solid content using ion-exchange water.
〔製造例Ａ−４〕（重合体Ａ−４の製造）
攪拌機付きガラス製反応容器（四つ口フラスコ）に水３３３ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３：新中村化学製ＮＫエステルＭ２３０Ｇ）３００ｇ、メタクリル酸（試薬：和光純薬工業（株））６９．７ｇ、及びメルカプトプロピオン酸６．３ｇを水２００ｇに混合溶解した溶液と、過硫酸アンモニウム１２．３ｇを水４５ｇに溶解した溶液の２者を、それぞれ１．５時間かけて上記反応容器中に滴下した。その後、１時間熟成し、さらに過硫酸アンモニウム４．９ｇを水１５ｇに溶解した溶液を３０分かけて滴下し、引き続き１．５時間熟成した。この一連の間の反応系の温度は８０℃に保たれた。熟成終了後に４０℃以下に冷却した後、４８重量％水酸化ナトリウム溶液５０．２ｇで中和し、重量平均分子量４３０００の重合体Ａ−４を得た。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-4] (Production of Polymer A-4)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 333 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 300 g of ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), 69.7 g of methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.), and 6.3 g of mercaptopropionic acid A solution prepared by mixing and dissolving 200 g of water in 200 g of water and a solution prepared by dissolving 12.3 g of ammonium persulfate in 45 g of water were dropped into the reaction vessel over 1.5 hours. Thereafter, the mixture was aged for 1 hour, and a solution obtained by dissolving 4.9 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 50.2 g of a 48 wt% sodium hydroxide solution to obtain a polymer A-4 having a weight average molecular weight of 43,000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.
〔製造例Ａ−５〕（重合体Ａ−５の製造）
攪拌機付きガラス製反応容器（四つ口フラスコ）に水１９８ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３：新中村化学製ＮＫエステルＭ２３０Ｇ）３００ｇ、アクリル酸（試薬：和光純薬工業（株）純度：９８％）５９．５ｇ、及びメルカプトプロピオン酸６．３ｇを水２００ｇに混合溶解した溶液と、過硫酸アンモニウム１２．３ｇを水４５ｇに溶解した溶液の２者を、それぞれ１．５時間かけて上記反応容器中に滴下した。その後、１時間熟成し、さらに過硫酸アンモニウム４．９ｇを水１５ｇに溶解した溶液を３０分かけて滴下し、引き続き１．５時間熟成した。この一連の間の反応系の温度は８０℃に保たれた。熟成終了後に４０℃以下に冷却した後、４８重量％水酸化ナトリウム溶液５０．２ｇで中和し、重量平均分子量４６０００の重合体Ａ−５を得た。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-5] (Production of Polymer A-5)
198 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 300 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical), acrylic acid (reagent: Wako Pure Chemical Industries, Ltd. purity: 98%) 59.5 g, and mercaptopropion Two solutions, a solution in which 6.3 g of acid was mixed and dissolved in 200 g of water and a solution in which 12.3 g of ammonium persulfate was dissolved in 45 g of water, were dropped into the reaction vessel over 1.5 hours. Thereafter, the mixture was aged for 1 hour, and a solution obtained by dissolving 4.9 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 50.2 g of a 48 wt% sodium hydroxide solution to obtain a polymer A-5 having a weight average molecular weight of 46000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.
〔製造例Ａ−６〕（重合体Ａ−６の製造）
攪拌機付きガラス製反応容器（四つ口フラスコ）に水２２５ｇ、及びポリオキシエチレン（エチレンオキシドの平均付加モル数３０）アリルエーテル３００ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。マレイン酸（試薬：和光純薬工業（株）純度：９９％）４７．４ｇ、及びメルカプトプロピオン酸３．７ｇを水１３７ｇに混合溶解した溶液と、過硫酸アンモニウム７．１ｇを水９０ｇに溶解した溶液の２者を、それぞれ２．５時間かけて上記反応容器中に滴下した。その後、２時間熟成し、さらに過硫酸アンモニウム２．８ｇを水４５ｇに溶解した溶液を６０分かけて滴下し、引き続き２時間熟成した。この一連の間の反応系の温度は８０℃に保たれた。熟成終了後に４０℃以下に冷却した後、４８重量％水酸化ナトリウム溶液２６．６ｇで中和し、重量平均分子量３１０００の重合体Ａ−６を得た。その後、イオン交換水を用いて固形分２０重量％に調整した。
[Production Example A-6] (Production of Polymer A-6)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 225 g of water and 300 g of polyoxyethylene (average added mole number of ethylene oxide: 30) allyl ether, and purged with nitrogen while stirring, up to 80 ° C. in a nitrogen atmosphere. The temperature rose. A solution in which 47.4 g of maleic acid (reagent: Wako Pure Chemical Industries, Ltd. purity: 99%) and 3.7 g of mercaptopropionic acid are mixed and dissolved in 137 g of water, and a solution in which 7.1 g of ammonium persulfate is dissolved in 90 g of water The two were dropped into the reaction vessel over 2.5 hours. Thereafter, the mixture was aged for 2 hours, and a solution obtained by dissolving 2.8 g of ammonium persulfate in 45 g of water was added dropwise over 60 minutes, followed by aging for 2 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of aging, the mixture was cooled to 40 ° C. or lower and neutralized with 26.6 g of a 48 wt% sodium hydroxide solution to obtain a polymer A-6 having a weight average molecular weight of 31,000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.
これらの重合体の組成及び重量平均分子量（Ｍｗ）を表１にまとめた。 The compositions and weight average molecular weights (Mw) of these polymers are summarized in Table 1.
表中の記号は以下のものである。表中、（ ）内の数字はＥＯ平均付加モル数である
・Ｍｗ：重量平均分子量
The symbols in the table are as follows. In the table, the numbers in parentheses are EO average added moles. Mw: weight average molecular weight
〔試験例１〕
以下の使用材料を以下の配合量で用いて、一括仕込みし、ボールミルにより粉砕してセメントを得た。得られたセメントを用いて調製した表２の配合（１）のモルタルについて、モルタルフロー及び強度を以下のように評価した。結果を表３に示す。
[Test Example 1]
The following materials were used in the following blending amounts, and charged in a lump and pulverized with a ball mill to obtain cement. About the mortar of the mixing | blending (1) of Table 2 prepared using the obtained cement, the mortar flow and intensity | strength were evaluated as follows. The results are shown in Table 3.
（１−１）使用材料
・クリンカー：石灰石、粘土、けい石、酸化鉄原料等を組み合わせて焼成したものを、クラッシャー及びグラインダーにより粗粉砕し、普通ポルトランドセメント用クリンカー（目開き３．５mmふるい通過品）を得た。成分は、ＣａＯ：６５％、ＳｉＯ2：２２％、Ａｌ2Ｏ3：５％、Ｆｅ2Ｏ3：３％、ＭｇＯ他：３％（重量基準）であった。
・二水石膏：二水石膏（ＳＯ3量４４．１３％）
・粉砕助剤：表３参照
(1-1) Materials used ・ Clinker: A combination of limestone, clay, silica, iron oxide raw materials, etc., baked roughly with a crusher and grinder, and ordinary Portland cement clinker (passing through a 3.5 mm mesh sieve) Product). The components were CaO: 65%, SiO 2 : 22%, Al 2 O 3 : 5%, Fe 2 O 3 : 3%, MgO and others: 3% (by weight).
・ Dihydrate gypsum: Dihydrate gypsum (SO 3 amount 44.13%)
・ Crushing aid: see Table 3
（１−２）配合量
・クリンカー：１０００ｇ（粗粉砕後の目開き３．５ｍｍふるい通過品）
・二水石膏：３８．５ｇ、添加ＳＯ3量を１．７％とした（１０００ｇ×１．７％／４４．１３％＝３８．５ｇ）
・粉砕助剤：表３の化合物を、水硬性化合物（クリンカー）１００重量部に対して、０．０８重量部（各成分の合計量として）使用した。なお、表３の比率で水に溶解する化合物は水溶液として用い、水に溶解しない化合物は、当該化合物と水とを別々に表３の比率で合計量が上記使用量となるように添加した。
(1-2) Blending amount / Clinker: 1000 g (product having a sieve opening of 3.5 mm after coarse pulverization)
・ Dihydrate gypsum: 38.5 g, and the amount of added SO 3 was 1.7% (1000 g × 1.7% / 44.13% = 38.5 g)
-Grinding aid: 0.08 weight part (as total amount of each component) of the compound of Table 3 was used with respect to 100 weight part of hydraulic compounds (clinker). In addition, the compound which melt | dissolves in water by the ratio of Table 3 was used as aqueous solution, and the compound which does not melt | dissolve in water was added so that the total amount may become the said usage-amount by the ratio of Table 3 separately in the said compound and water.
（１−３）水硬性化合物の粉砕
株式会社セイワ技研製ＡＸＢ−１５を用い、ステンレスポット容量は１８リットル（外径３００ｍｍ）とし、３０ｍｍφ（呼び１・３／１６）７０個、２０ｍｍφ（呼び３／４）７０個の合計１４０個のステンレスボールを使用し、ボールミルの回転数は、４５ｒｐｍとした。また粉砕途中で粉砕物を排出する時間を１分間と設定した。７５〜１００分の粉砕時間で、３３００±１００ｃｍ2／ｇのブレーン値を有するセメントを得た。
(1-3) Crushing of hydraulic compound Using AXB-15 manufactured by Seiwa Giken Co., Ltd., the capacity of the stainless steel pot is 18 liters (outer diameter 300 mm), 70 pieces of 30 mmφ (nominal 1/3/16), 20 mmφ (nominal 3) / 4) A total of 140 stainless steel balls of 70 were used, and the rotation speed of the ball mill was 45 rpm. The time for discharging the pulverized material during the pulverization was set to 1 minute. A cement having a brane value of 3300 ± 100 cm 2 / g was obtained with a grinding time of 75 to 100 minutes.
（１−４）モルタルフロー及び強度試験
モルタルフローは、セメントの物理試験方法（ＪＩＳ Ｒ ５２０１）フロー試験に従った。また、強度は、セメントの物理試験方法（ＪＩＳ Ｒ ５２０１）附属書２（セメントの試験方法−強さの測定）に従った。なお、モルタルの配合は、下記表１の配合（１）とした。
(1-4) Mortar flow and strength test The mortar flow followed the cement physical test method (JIS R 5201) flow test. Further, the strength was in accordance with cement physical test method (JIS R 5201), Annex 2 (cement test method-measurement of strength). The mortar was blended as shown in Table 1 below (1).
・Ｗ：水道水
・Ｃ：前記（１−３）で得られたブレーン値３３００±１００ｃｍ2／ｇのセメント
・Ｓ：セメントの物理試験方法（ＪＩＳ Ｒ ５２０１）附属書２（セメントの試験方法−強さの測定）に従った標準砂
W: tap water C: cement with a brane value of 3300 ± 100 cm 2 / g obtained in (1-3) S: physical test method for cement (JIS R 5201) Annex 2 (test method for cement— Standard sand according to strength measurement)
〔実施例１〕
表５の粉砕助剤を用いて試験例１と同様に水硬性化合物を粉砕してセメントを得た。ただし、比較例１−１は粉砕助剤としてジエチレングリコールのみを用い、また、比較例１−１８は粉砕助剤を使用せずに、それぞれ水硬性化合物の粉砕を行った。得られたセメント及び上記重合体を用いて調製した表４の配合（２）のモルタルについて、モルタルフロー２００±２０ｍｍを目標に重合体の添加量を調整し、モルタルフロー及び強度を試験例１と同様に評価した。結果を表５に示す。
[Example 1]
Cement was obtained by pulverizing the hydraulic compound in the same manner as in Test Example 1 using the pulverization aid of Table 5. However, Comparative Example 1-1 used only diethylene glycol as a pulverization aid, and Comparative Example 1-18 pulverized a hydraulic compound without using a pulverization aid. About the mortar of the mixing | blending (2) of Table 4 prepared using the obtained cement and the said polymer, the addition amount of a polymer was adjusted for the purpose of mortar flow 200 +/- 20mm, and mortar flow and intensity | strength were set to Test Example 1. Evaluation was performed in the same manner. The results are shown in Table 5.
・Ｗ：水道水
・Ｃ：試験例１の（１−３）と同様の方法で得られたブレーン値３３００±１００ｃｍ2／ｇのセメント
・Ｓ：城陽産山砂（目開き３．５ｍｍふるい通過品）
W: Tap water C: Cement with a brane value of 3300 ± 100 cm 2 / g obtained by the same method as in (1-3) of Test Example 1 S: Mountain sand from Joyo (mesh passing through 3.5 mm sieve) )
表中、重合体の添加量は、セメントに対する有効分の重量％である。 In the table, the amount of the polymer added is the weight percent of the effective amount relative to the cement.
試験例１の配合１は流動性を有しており、モルタルの製造の際に分散剤を必要としない配合である。一方、実施例１の配合２は分散剤なしでは流動性の乏しい配合である。グリセリンと水とを粉砕助剤とした水硬性粉体の使用に関して、試験例１（試験例１−１３）では、７日強度が一般に用いられるジエチレングリコールと水とを粉砕助剤とした場合（試験例１−２）よりも１Ｎ／ｍｍ2劣っている。しかし、モルタルの製造の際に分散剤として一般式（１）で表される重合体を使用する実施例１では（実施例１−１）、いずれもジエチレングリコール（比較例１−１〜１−５）よりも７日強度に優れ、グリセリンと水とを粉砕助剤とした水硬性粉体と一般式（１）で表される重合体の併用の効果があることがわかる。しかも、グリセリンをモルタル調製時に添加した比較例１−１８では７日強度が低いことから、グリセリンと水（グリセリン系粉砕助剤）は実施例のように粉砕時に用いる必要があり、添加時期が重要であることがわかる。 Formulation 1 of Test Example 1 has fluidity and does not require a dispersant when producing mortar. On the other hand, Formulation 2 of Example 1 is a formulation with poor fluidity without a dispersant. Regarding the use of hydraulic powder with glycerin and water as a grinding aid, in Test Example 1 (Test Example 1-13), when diethylene glycol and water generally used for 7 days are used as grinding aid (test It is inferior to Example 1-2) by 1 N / mm 2 . However, in Example 1 in which the polymer represented by the general formula (1) is used as a dispersant in the production of mortar (Example 1-1 ) , both are diethylene glycol (Comparative Examples 1-1 to 1-5). ) Is superior in strength to 7 days, and it can be seen that there is an effect of the combined use of the hydraulic powder using glycerin and water as a grinding aid and the polymer represented by the general formula (1). Moreover, in Comparative Example 1-18 in which glycerin was added at the time of mortar preparation, the strength was low for 7 days. Therefore, it is necessary to use glycerin and water (glycerin-based grinding aid) at the time of grinding as in Examples, and the timing of addition is important. It can be seen that it is.
Claims (6)
下記の一般式（１）で表される単量体由来の構成単位１と下記の一般式（２）で表される単量体由来の構成単位２とを有する重合体と、
水と、
を混合して水硬性組成物を得る、水硬性組成物の製造方法であり、
前記水硬性化合物の粉砕の際の、グリセリンの存在量が、水硬性化合物１００重量部に対して、０．００１〜０．２重量部であり、水及び／又は炭素数１〜４の１価アルコールの存在量が、水硬性化合物１００重量部に対して、０．００１〜０．２重量部である、水硬性組成物の製造方法。
〔式中、Ｒ 1 は水素原子、Ｒ 2 は水素原子又はメチル基、Ｒ3は水素原子、ＡＯは炭素数２〜４のオキシアルキレン基又はオキシスチレン基、ｐは１の数、ｑは０の数、ｒはＡＯの平均付加モル数であり、１１０〜１５０の数、Ｒ4は水素原子又は炭素数１〜１８のアルキル基を表す。〕
〔式中、Ｒ5〜Ｒ7は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよく、その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の数を表す。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属（1/2原子）、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基を表す。〕 Hydraulic powder obtained by pulverizing a hydraulic compound in the presence of glycerin and water and / or a monohydric alcohol having 1 to 4 carbon atoms,
A polymer having a structural unit 1 derived from a monomer represented by the following general formula (1) and a structural unit 2 derived from a monomer represented by the following general formula (2);
water and,
Is a method for producing a hydraulic composition, wherein a hydraulic composition is obtained by mixing
The amount of glycerin in the pulverization of the hydraulic compound is 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the hydraulic compound, and water and / or monovalent having 1 to 4 carbon atoms. The manufacturing method of the hydraulic composition whose abundance of alcohol is 0.001-0.2 weight part with respect to 100 weight part of hydraulic compounds.
Wherein, R 1 represents a hydrogen atom, R 2 is a hydrogen atom or a methyl group, R 3 is hydrogen atom, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, p is the number of 1, q is the number of 0, r is the average addition mole number of AO, the number of 110 to 150, R 4 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]
Wherein, R 5 to R 7 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or another (CH 2) s COOM 2 and anhydrous In this case, M 1 and M 2 of those groups are not present. s represents the number of 0-2. M 1 and M 2 each represent a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
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