JPH0153218B2 - - Google Patents
Info
- Publication number
- JPH0153218B2 JPH0153218B2 JP56189902A JP18990281A JPH0153218B2 JP H0153218 B2 JPH0153218 B2 JP H0153218B2 JP 56189902 A JP56189902 A JP 56189902A JP 18990281 A JP18990281 A JP 18990281A JP H0153218 B2 JPH0153218 B2 JP H0153218B2
- Authority
- JP
- Japan
- Prior art keywords
- less
- water
- components
- cement
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004568 cement Substances 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 11
- 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 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229920005610 lignin Polymers 0.000 claims 1
- 239000000047 product Substances 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- 239000004567 concrete Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229920001732 Lignosulfonate Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- -1 polycyclic aromatic compounds Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NIMLCWCLVJRPFY-UHFFFAOYSA-N 1-(5-bicyclo[2.2.1]hept-2-enyl)ethanone Chemical compound C1C2C(C(=O)C)CC1C=C2 NIMLCWCLVJRPFY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 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
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-M naphthalene-2-sulfonate Chemical compound C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-M 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
本発明は、セメントペースト、モルタル、コン
クリートなどの水硬性材料のセメント分散剤、さ
らに詳しくは、ナフタレンスルホン酸ホルマリン
縮合物の塩、低分子量体の含有率を減少させたリ
グニンスルホン酸塩を含むパルプ排液処理物、及
びエチレン性不飽和ジカルボン酸と二重結合を有
する炭化水素系化合物の共重合物の塩を主成分と
して含有するか、またはこれらの成分にさらに消
泡剤を加えたものを主成分として含有してなる、
高減水性と持続性のあるワーカビリチーと高強度
をもたらすセメント分散剤に関する。
一般に、セメントを使用するペーストやモルタ
ル、コンクリートなどを製造する際にその流動性
を改善するために分散剤を使用するが、その分散
剤としては、例えばリグニンスルホン酸塩を主体
とするもの、β−ナフタレンスルホン酸塩ホルマ
リン縮合物を主体とするもの、スルホン酸残基を
有するメラミンのホルマリン高縮合物を主体とす
るものなどがあるが、これらは次のような欠点が
ある。
すなわち、リグニンスルホン酸塩を主体とする
ものは、短期強度の発現が悪いので、塩化カルシ
ウム、硫酸ソーダ、アミン類などと併用してこれ
を改善しているが、その反面、鉄筋が腐食したり
冬期においては結晶が析出したり、さらには空気
連行性、硬化遅延性、偽凝結などがあるので、こ
れを多量に使用して水量を減少させることはでき
ない。
また、β−ナフタレンスルホン酸塩ホルマリン
縮合物やスルホン酸残基を有するメラミンのホル
マリン高縮合物を主体とするものは、低い単位水
量で良好なワーカビリチーをもたらすことができ
るが、それには添加量を多くしなければならず、
しかもワーカビリチーは短時間のうちに大きく低
下してしまうので、その使用に際しては十分な注
意が必要である。たとえば、これらの添加剤を用
いる場合には混練後のコンクリートは急速にワー
カビリチーが低下するので、きわめて短時間のう
ちに取扱い作業を完了する必要がある。通常の生
コンクリートの製造において、この添加剤を用い
た場合コンクリートミキサー車などによる運搬が
できない。さらには、工場においてコンクリート
製品を製造する場合でも混練後のコンクリートの
ワーカビリチーの低下に十分注意する必要があ
る。
本発明は、これらの欠点を解決することを目的
とするものであつて、第１発明は、ナフタレンス
ルホン酸ホルマリン縮合物の塩、全固形分中の分
子量2000以下の成分の含有率が30％以下であるリ
グニンスルホン酸塩を主成分としてなるパルプ排
液処理物、及びエチレン性不飽和ジカルボン酸と
二重結合を有する炭化水素系化合物との共重合物
の水溶性塩を主成分として含有してなるセメント
分散剤であり、第２発明は、これらの成分にさら
に消泡剤を加えたものを主成分として含有してな
るセメント分散剤である。
以下、詳しく本発明について説明する。
先ず、本発明に係るナフタレンスルホン酸ホル
マリン縮合物の塩について説明する。これは、ナ
フタレンスルホン酸の単独縮合物に限られるもの
ではなく、ナフタレン、アルキルナフタレン、ア
ントラセンなどの多環芳香族化合物又はそのスル
ホン酸化合物やベンゼン、トルエン、フエノー
ル、安息香酸などのベンゼン誘導体又はそのスル
ホン酸化合物などから選ばれた１種又は２種以上
の化合物とのホルマリン共縮合物であつてもよ
い。これらのホルマリン縮合物の塩としては、ア
ルカリ塩及び／又はアルカリ土類塩であり、具体
的にはナトリウム塩、カリウム塩、カルシウム塩
およびこれらの混合塩である。
ナフタレンスルホン酸ホルマリン縮合物の塩の
市販品としては、商品名「マイテイ」（花王石鹸
(株)製）、商品名「ポールフアイン」（竹本油脂(株)
製）、商品名「セロフロ−R155」（第一工業製薬
(株)製）などがある。
次に、全固形分中分子量2000以下の成分の含有
率を30％以下に減少させたリグニンスルホン酸塩
を主成分としてなるパルプ排液処理物（以下、単
にパルプ排液処理物という）について説明する。
本発明において、パルプ排液処理物に含まれる
分子量2000以下の成分の含有率を30％以下に限定
した理由は、分子量2000以下の成分の含有率が30
％を越えるものをセメント分散剤として使用した
場合は硬化遅延性が大きく、低分散性となること
にもとづくものである。なお、リグニンスルホン
酸塩の分子量は分子量既知の標準ポリスチレンス
ルホン酸を基準に用いて親水性処理したシリカゲ
ルによるゲルパーミエイシヨンクロマトグラフに
より測定することができる。
このようなパルプ排液処理物を得るには、パル
プ排液を原料とし、これに種々の化学的または物
理的処理をして低分子成分を除去すればよい。そ
の原料としては亜硫酸パルプ排液が好ましく、か
つ針葉樹系パルプ排液が好ましい。また、低分子
成分を除去する方法としては、実験室的にはセル
ロース膜を用いた透析法などを採用できるが工業
的には限外過法などの方法が好ましい。特に限
外過法によつてパルプ排液を処理する場合は任
意の成分をその分子の大きさにより分取できるの
で有利である。
次に、エチレン性不飽和ジカルボン酸と二重結
合を有する炭化水素系化合物との共重合物の水溶
性塩（以下、多価カルボン酸共重合物という）に
ついて説明する。これは、前記２者の成分と共働
してワーカビリチーの経時低下を相乗的に防止す
るために必要な成分であり、エチレン性不飽和ジ
カルボン酸と二重結合を有する炭化水素系化合物
とを、好ましくは１：１〜３：１のモル比で混合
したものを重合開始剤を用いて共重合し、得られ
た共重合体をナトリウム、カリウムなどのアルカ
リ金属の塩基やアンモニアなどで加水分解する
か、又はこれらを部分的にエステル化することに
より得られるものである。
エチレン性不飽和ジカルボン酸としては、マレ
イン酸、イタコン酸、シトラコン酸などがあげら
れるが、マレイン酸はその誘導体が好ましく、ま
た、二重結合を有する炭化水素系化合物として
は、スチレン、メチルスチレンなどのスチレン系
化合物やC4〜C16の鎖状及び／又は環状のオレフ
イン炭化水素類、具体的には、ブテン−１、ブテ
ン−２、イソブチレン、ペンテン−１、ペンテン
−２、２−メチル−ブテン−１、２−メチル−ブ
テン−２、４−メチル−ペンテン−１、ヘキセン
−１などやシクロブテン、シクロペンテン、シク
ロヘキセン、シクロヘプテン、シクロオクテン、
シクロペンタジエン、ジシクロペンタジエン、２
−エチル−５−ノルボルネン、２−シアノ−５−
ノルボルネン、２−アセチル−５−ノルボルネン
などがあげられる。これらの炭化水素系化合物の
なかでスチレン系化合物は効果が大きい。
ナフタレンスルホン酸ホルマリン縮合物の塩と
パルプ排液処理物の割合は、高減水性と持続性の
あるワーカビリチーすなわち流動性の経時低下防
止、および強度発現性の向上の点から、前者に対
する後者の重量比を95対５から５対95とするのが
望ましい。その理由は、ナフタレンスルホン酸ホ
ルマリン縮合物の塩の割合がこれよりも多くなる
とワーカビリチーの持続性が悪く流動性の経時低
下が顕著となり、また、パルプ排液処理物の割合
がこれよりも多くなると硬化遅延して強度発現が
不十分となるからである。また、多価カルボン酸
共重合物の割合は、重量で、前２者の成分合計量
95〜５に対し５〜95、好ましくは95〜50に対し５
〜50の範囲である。多価カルボン酸共重合物の割
合がこれよりも著しく多かつたり少なかつたりす
ると、強度発現が不十分となつたり偽凝結するよ
うになる。
以上のナフタレンスルホン酸ホルマリン縮合物
の塩とパルプ排液処理物と多価カルボン酸共重合
物を主成分として含有してなるセメント分散剤を
用いれば、水硬性材料に高減水性と持続性のある
ワーカビリチーを付与し、硬化遅延もほとんどな
い高強度な水硬性材料を製造することができると
いう効果がある。
第２発明は、第１発明のセメント分散剤にさら
に消泡剤を含有させたものであり、それによつて
第１発明のセメント分散剤の特性を保持したまま
でさらに強度発現を良好とすることができる。
本発明で用いられる消泡剤としては多価アルコ
ール脂胞酸の部分エステル、ポリプロピレンオキ
サイドとポリエチレンオキサイドのブロツクポリ
マー、高級アルコール、シリコーンおよびこれら
の混合物があげられ、具体的な市販品としては、
日本油脂(株)商品名「デイスホーム」東芝シリコー
ン社商品名「TSA732」などがあげられる。
本発明のセメント分散剤のセメントに対する添
加率は通常0.05〜１％程度である。また、本発明
のセメント分散剤は従来からセメント用混和剤と
して一般に用いられている減水剤、遅延剤、硬化
促進剤、AE剤、AE減水剤、膨張剤、などと併用
しても何ら差支えはない。
現在、水硬性材料コンシステンシーの経時低下
を防止するためのよりすぐれた添加剤の開発が強
く要望されており、本発明はこれに応えたもので
ある。従つて、本発明のセメント分散剤の添加時
期は、前添加法、後添加法、分割添加法のいずれ
でもよく、特に前添加法により使用する場合は有
利である。なお、前添加法とは水硬性材料の混練
前または混練中にセメント分散剤を添加する方
法、後添加法とは水硬性材料を短時間混練した後
セメント分散剤を添加する方法、分割添加法とは
セメント分散剤を一定時間ごとに分割して水硬性
材料に添加する方法である。
水硬性材料を調合するセメントとしては、普
通、早強、超早強、中庸熱、白色のポルトランド
セメント、シリカ、フライフツシユ、高炉水砕ス
ラグなどを配合した混合セメント、膨張セメン
ト、カルシウムアルミネートと石コウを存在させ
た急硬セメント、アルミナセメント、さらには高
炉水砕スラグとアルカリ金属又はアルカリ土類金
属の水酸化物、酸化物、炭酸塩、硫酸塩などのア
ルカリ刺激剤からなるセメントなどがあげられ
る。
本発明のセメント分散剤を添加した水硬性材料
は土木用建築用などの場所打ちコンクリート、並
びにつき固め、振動締め固めもしくは遠心力締め
固め成形したのち常温養生又は蒸気養生もしくは
オートクレーブ養生などの加熱養生を行なつて生
産される、例えば、パイル、ポール、コンクリー
ト管、ボツクスカルバート、Ｕ字溝、鋼管コンク
リート複合体、ブロツクなどの工場製品製造用コ
ンクリートとして使用される。
以下、実施例をあげて本発明を説明する。な
お、本明細書記載の部及び％はいずれも重量基準
で示した。
実施例 １
第１表に示した添加剤を所定量の水に溶解し、
これに普通ポルトランドセメント2.0Kg、相模川
産川砂6.0Kgを加えハンドミキサーを用いて30℃
で１分間混合しモルタルを混練した。このモルタ
ルの練り上り直後のミニスランプフローを測定
し、フロー値が260mmとなるまで水量を変化させ
てモルタルを再混練し、このときの所要水量から
水セメント比Ｗ／Ｃを求めて第１表に示した。混
練直後のフロー値が260mmとなつたモルタルはフ
ロー測定後静置し、15分毎にハンドミキサーによ
り15秒間混練しミニスランプフローを測定した。
ミニスランプフローは高さ15cm（上開口部直経５
cm、下開口部直経10cm）のスランプコーンにモル
タルを充てんした後すみやかにスランプコーンを
引き上げ、このときのモルタルの広がりを測定し
て求めた。その結果を第１表に示す。
第１表から明かな通り、実施例は比較例に比べ
て減水性、フローの経時変化、強度発現性の性能
のバランスにおいてすぐれていることがわかる。
なお、第１表で示した添加剤記号は次の成分を
表わすものである。
Ｎ：β−ナフタレンスルホン酸ホルマリン縮合物
のソーダ塩
Ｌ：限外過したサルフアイトパルプ排液（分離
限界MW6000の限外過膜使用）
Ｘ：モル比１：１のアミレンと無水マレイン酸の
共重合物のソーダ塩
Ｙ：モル比１：１のスチレンと無水マレイン酸の
共重合物のソーダ塩
Ｓ： 市販のシリコーン系消泡剤
（商品名「TSA732」）
The present invention is a cement dispersant for hydraulic materials such as cement paste, mortar, and concrete, and more specifically, a pulp containing a salt of a naphthalene sulfonic acid formalin condensate and a lignin sulfonate with a reduced content of low molecular weight substances. A wastewater treatment product containing as a main component a salt of a copolymer of an ethylenically unsaturated dicarboxylic acid and a hydrocarbon compound having a double bond, or a product in which an antifoaming agent is further added to these components. Contains as a main component,
This product relates to a cement dispersant that provides high water-reducing properties, sustainable workability, and high strength. Generally, dispersants are used to improve the fluidity of pastes, mortars, concrete, etc. using cement. - There are those mainly based on a formalin condensate of naphthalene sulfonate, and those mainly based on a high formalin condensate of melamine having a sulfonic acid residue, but these have the following drawbacks. In other words, lignin sulfonate-based products have poor short-term strength, so they are used in combination with calcium chloride, sodium sulfate, amines, etc. to improve this, but on the other hand, they may corrode the reinforcing steel. In winter, crystals precipitate, and furthermore, it has air entrainment, curing retardation, and false setting, so it cannot be used in large quantities to reduce the amount of water. In addition, products mainly composed of formalin condensates of β-naphthalene sulfonate and formalin high condensates of melamine having sulfonic acid residues can provide good workability with a small amount of water per unit; have to do more,
Moreover, workability decreases significantly in a short period of time, so sufficient care must be taken when using it. For example, when these additives are used, the workability of the concrete after mixing rapidly decreases, so it is necessary to complete the handling work within an extremely short period of time. When this additive is used in the production of normal ready-mixed concrete, it cannot be transported by concrete mixer trucks or the like. Furthermore, even when manufacturing concrete products in a factory, it is necessary to pay sufficient attention to the reduction in workability of concrete after mixing. The present invention aims to solve these drawbacks, and the first invention is a salt of naphthalene sulfonic acid formalin condensate, the content of components having a molecular weight of 2000 or less in the total solid content is 30%. Contains as a main component a treated pulp effluent containing the following lignin sulfonate as a main component, and a water-soluble salt of a copolymer of an ethylenically unsaturated dicarboxylic acid and a hydrocarbon compound having a double bond. The second invention is a cement dispersant comprising as a main component an antifoaming agent added to these components. The present invention will be explained in detail below. First, the salt of the naphthalene sulfonic acid formalin condensate according to the present invention will be explained. This is not limited to single condensates of naphthalene sulfonic acid, but also polycyclic aromatic compounds such as naphthalene, alkylnaphthalene, and anthracene, or their sulfonic acid compounds, and benzene derivatives such as benzene, toluene, phenol, benzoic acid, etc. It may be a formalin cocondensate with one or more compounds selected from sulfonic acid compounds and the like. Salts of these formalin condensates include alkali salts and/or alkaline earth salts, specifically sodium salts, potassium salts, calcium salts, and mixed salts thereof. As a commercially available salt of naphthalene sulfonic acid formalin condensate, the product name ``Mighty'' (Kao Soap
(manufactured by Takemoto Yushi Co., Ltd.), product name: "Pole Huain" (manufactured by Takemoto Yushi Co., Ltd.)
(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), product name “Ceroflo-R155” (Daiichi Kogyo Seiyaku Co., Ltd.)
Co., Ltd.). Next, we will explain the pulp effluent treatment product (hereinafter simply referred to as the pulp effluent treatment product), which is mainly composed of lignin sulfonate in which the content of components with a molecular weight of 2000 or less in the total solid content is reduced to 30% or less. do. In the present invention, the reason why the content of components with a molecular weight of 2,000 or less in the treated pulp waste liquid is limited to 30% or less is that the content of components with a molecular weight of 2,000 or less is 30% or less.
This is based on the fact that when a cement dispersant containing more than 5% of the total amount of carbon dioxide is used as a cement dispersant, hardening retardation is large and dispersibility becomes low. The molecular weight of the lignin sulfonate can be measured by gel permeation chromatography using silica gel that has been subjected to hydrophilic treatment using standard polystyrene sulfonic acid with a known molecular weight as a standard. In order to obtain such a treated pulp waste liquid, the pulp waste liquid may be used as a raw material, and it may be subjected to various chemical or physical treatments to remove low molecular components. As the raw material, sulfite pulp waste liquid is preferable, and coniferous pulp waste liquid is preferable. Further, as a method for removing low molecular weight components, a dialysis method using a cellulose membrane can be employed in the laboratory, but a method such as an ultrafiltration method is preferable in an industrial setting. In particular, when pulp wastewater is treated by ultrafiltration, it is advantageous because any component can be fractionated according to its molecular size. Next, a water-soluble salt of a copolymer of an ethylenically unsaturated dicarboxylic acid and a hydrocarbon compound having a double bond (hereinafter referred to as a polyhydric carboxylic acid copolymer) will be explained. This is a necessary component to synergistically prevent the deterioration of workability over time by working together with the above two components. A mixture preferably in a molar ratio of 1:1 to 3:1 is copolymerized using a polymerization initiator, and the resulting copolymer is hydrolyzed with an alkali metal base such as sodium or potassium or ammonia. or by partially esterifying these. Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, itaconic acid, and citraconic acid. Maleic acid is preferably a derivative thereof, and hydrocarbon compounds having double bonds include styrene, methylstyrene, etc. styrenic compounds and C4 to C16 chain and/or cyclic olefin hydrocarbons, specifically butene-1, butene-2, isobutylene, pentene-1, pentene-2, 2-methyl- Butene-1, 2-methyl-butene-2, 4-methyl-pentene-1, hexene-1, etc., cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,
Cyclopentadiene, dicyclopentadiene, 2
-ethyl-5-norbornene, 2-cyano-5-
Examples include norbornene and 2-acetyl-5-norbornene. Among these hydrocarbon compounds, styrene compounds are highly effective. The ratio of the salt of the naphthalene sulfonic acid formalin condensate to the treated pulp wastewater is determined by the weight of the latter relative to the former, from the viewpoint of high water-reducing properties and sustainable workability, that is, prevention of fluidity decline over time, and improvement of strength development. A ratio of 95:5 to 5:95 is desirable. The reason for this is that when the proportion of the salt of the naphthalene sulfonic acid formalin condensate exceeds this range, the sustainability of workability deteriorates and the fluidity decreases over time, and when the proportion of the pulp wastewater treated product exceeds this range, This is because curing is delayed and strength development becomes insufficient. In addition, the proportion of the polyhydric carboxylic acid copolymer is the total amount of the former two components by weight.
5 to 95 to 95 to 5, preferably 5 to 95 to 50
~50 range. If the proportion of the polyhydric carboxylic acid copolymer is significantly higher or lower than this, the strength development will be insufficient or false coagulation will occur. If a cement dispersant containing the above-mentioned naphthalene sulfonic acid formalin condensate salt, pulp wastewater treatment product, and polyhydric carboxylic acid copolymer as main components is used, high water-reducing properties and sustainability can be achieved in hydraulic materials. It has the effect of being able to produce a high-strength hydraulic material that provides a certain level of workability and has almost no curing delay. The second invention is the cement dispersant of the first invention further containing an antifoaming agent, thereby further improving the strength development while retaining the characteristics of the cement dispersant of the first invention. Can be done. Antifoaming agents used in the present invention include partial esters of polyhydric alcohol fatty acids, block polymers of polypropylene oxide and polyethylene oxide, higher alcohols, silicones, and mixtures thereof. Specific commercially available products include:
Examples include Nippon Oil & Fats Co., Ltd.'s product name ``Days Home'' and Toshiba Silicone Company's product name ``TSA732.'' The addition rate of the cement dispersant of the present invention to cement is usually about 0.05 to 1%. Furthermore, the cement dispersant of the present invention can be used in combination with water reducing agents, retarders, hardening accelerators, AE agents, AE water reducing agents, swelling agents, etc. that have been commonly used as admixtures for cement without any problem. do not have. Currently, there is a strong demand for the development of better additives to prevent the consistency of hydraulic materials from deteriorating over time, and the present invention meets this demand. Therefore, the cement dispersant of the present invention may be added by any of the pre-addition method, post-addition method, and divided addition method, and it is particularly advantageous to use the pre-addition method. The pre-addition method refers to a method in which a cement dispersant is added before or during the mixing of hydraulic materials, and the post-addition method refers to a method in which a cement dispersant is added after kneading hydraulic materials for a short time, and the divided addition method This is a method in which the cement dispersant is added to the hydraulic material in portions at regular intervals. The cement used to prepare hydraulic materials includes normal, early strength, ultra early strength, medium heat, white Portland cement, mixed cement containing silica, fried wood, granulated blast furnace slag, etc., expanded cement, calcium aluminate and stone. Examples include rapid hardening cement in which Kou is present, alumina cement, and cement made of granulated blast furnace slag and alkaline irritants such as hydroxides, oxides, carbonates, and sulfates of alkali metals or alkaline earth metals. It will be done. The hydraulic material to which the cement dispersant of the present invention has been added can be used as cast-in-place concrete for civil engineering and construction purposes, and after compaction, vibration compaction, or centrifugal force compaction, it is cured at room temperature, steam cured, or heated in an autoclave. It is used as concrete for manufacturing factory products such as piles, poles, concrete pipes, box culverts, U-shaped grooves, steel pipe concrete composites, and blocks. The present invention will be explained below with reference to Examples. Note that all parts and percentages described in this specification are expressed on a weight basis. Example 1 The additives shown in Table 1 were dissolved in a predetermined amount of water,
Add 2.0 kg of ordinary Portland cement and 6.0 kg of river sand from the Sagami River to this, and mix at 30°C using a hand mixer.
The mortar was kneaded by mixing for 1 minute. The mini-slump flow of this mortar was measured immediately after mixing, and the mortar was re-kneaded by varying the amount of water until the flow value reached 260 mm.The water-cement ratio W/C was calculated from the required water amount at this time and is shown in Table 1. It was shown to. The mortar with a flow value of 260 mm immediately after kneading was allowed to stand after flow measurement, and was kneaded for 15 seconds with a hand mixer every 15 minutes to measure mini-slump flow.
Mini slump flow is 15cm high (direct diameter of the upper opening 5cm)
After filling mortar into a slump cone with a diameter of 10 cm (diameter 10 cm from the bottom opening), the slump cone was immediately pulled up and the spread of the mortar was measured. The results are shown in Table 1. As is clear from Table 1, the Examples are superior to the Comparative Examples in terms of the balance of performance in water reduction, flow change over time, and strength development. The additive symbols shown in Table 1 represent the following components. N: Soda salt of β-naphthalenesulfonic acid formalin condensate L: Ultrafiltered sulfite pulp effluent (using an ultrafiltration membrane with a separation limit of MW 6000) Soda salt of polymer Y: Soda salt of a copolymer of styrene and maleic anhydride at a molar ratio of 1:1 S: Commercially available silicone antifoaming agent (trade name "TSA732")
【表】
実施例 ２
第２表に示す配合の添加剤を水6.24Kgに溶解
し、普通ポルトランドセメント12.0Kg、相模川産
川砂31.7Kg、相模川産川砂利（25mm以下）42.0Kg
に水6.3Kgを加え目標スランプ18cmのコンクリー
トを混練した。添加剤はあらかじめ練りまぜ水の
一部に加え最初に添加し、スランプは最終調整水
にて合わせた。混練直後のスランプ18cmのコンク
リートを静置し、20分毎に練り直しを行つてスラ
ンプを再測定し、経時変化を60分間にわたり測定
した。
第２表より、実施例は減水性、初期スランプ、
スランプの経時変化、強度発現性の性能のバラン
スにおいて比較例よりすぐれていることが明かで
ある。[Table] Example 2 Additives with the composition shown in Table 2 were dissolved in 6.24 kg of water, 12.0 kg of ordinary Portland cement, 31.7 kg of river sand from the Sagami River, and 42.0 kg of river gravel from the Sagami River (25 mm or less).
6.3 kg of water was added to mix concrete with a target slump of 18 cm. The additives were added in advance to a portion of the mixing water at the beginning, and the slump was adjusted using the final adjustment water. Immediately after mixing, concrete with a slump of 18 cm was allowed to stand, and the slump was re-measured every 20 minutes after being remixed every 20 minutes, and changes over time were measured over 60 minutes. From Table 2, Examples have water reduction properties, initial slump,
It is clear that the performance balance of slump change over time and strength development performance is superior to the comparative example.
【表】
ものである。
[Table] It is a thing.
Claims (1)
塩、全固形分中の分子量2000以下の成分の含有率
が30重量％以下であるリグニンスルホン酸を主成
分としてなるパルプ排液処理物、及びエチレン性
不飽和ジカルボン酸と二重結合を有する炭化水素
系化合物との共重合物の水溶性塩を主成分として
含有してなるセメント分散剤。 ２ ナフタレンスルホン酸ホルマリン縮合物の
塩、全固形分中の分子量2000以下の成分の含有率
が30重量％以下であるリグニンスルホン酸を主成
分としてなるパルプ排液処理物、エチレン性不飽
和ジカルボン酸と二重結合を有する炭化水素系化
合物との共重合物の水溶性塩、及び消泡剤を主成
分として含有してなるセメント分散剤。[Scope of Claims] 1. A treated pulp effluent mainly composed of a salt of a naphthalenesulfonic acid formalin condensate, ligninsulfonic acid in which the content of components with a molecular weight of 2000 or less in the total solid content is 30% by weight or less, and a cement dispersant containing as a main component a water-soluble salt of a copolymer of an ethylenically unsaturated dicarboxylic acid and a hydrocarbon compound having a double bond. 2 Salts of naphthalene sulfonic acid formalin condensates, treated pulp effluents whose main component is lignin sulfonic acid with a content of components with a molecular weight of 2000 or less in the total solid content of 30% by weight or less, ethylenically unsaturated dicarboxylic acids A cement dispersant comprising, as main components, a water-soluble salt of a copolymer of and a hydrocarbon compound having a double bond, and an antifoaming agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18990281A JPS5895634A (en) | 1981-11-28 | 1981-11-28 | Cement dispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18990281A JPS5895634A (en) | 1981-11-28 | 1981-11-28 | Cement dispersant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5895634A JPS5895634A (en) | 1983-06-07 |
| JPH0153218B2 true JPH0153218B2 (en) | 1989-11-13 |
Family
ID=16249106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18990281A Granted JPS5895634A (en) | 1981-11-28 | 1981-11-28 | Cement dispersant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5895634A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169960A (en) * | 1983-03-15 | 1984-09-26 | 花王株式会社 | Concrete additive and concrete slump loss prevention |
| JPS6051649A (en) * | 1983-08-31 | 1985-03-23 | 日本ゼオン株式会社 | Manufacture of cement set body |
| DE4018873A1 (en) * | 1990-06-13 | 1991-12-19 | Basf Ag | USE OF CONDENSATIONS BASED ON ARYLSULPHONIC ACIDS AND FORMALDEHYDE AS DISPERSIBLE AGENTS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51101024A (en) * | 1975-03-04 | 1976-09-07 | Nippon Zeon Co | SEMENTOYOKON WAZAI |
| JPS53145841A (en) * | 1977-05-25 | 1978-12-19 | Kobe Zairyo Kk | Water diminishing agent for concrete |
| JPS5551863A (en) * | 1978-10-06 | 1980-04-15 | Shinetsu Polymer Co | Production of string having core wire |
| JPS5696763A (en) * | 1979-12-28 | 1981-08-05 | Nisso Master Builders Kk | Cement dispersing agent composition |
-
1981
- 1981-11-28 JP JP18990281A patent/JPS5895634A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51101024A (en) * | 1975-03-04 | 1976-09-07 | Nippon Zeon Co | SEMENTOYOKON WAZAI |
| JPS53145841A (en) * | 1977-05-25 | 1978-12-19 | Kobe Zairyo Kk | Water diminishing agent for concrete |
| JPS5551863A (en) * | 1978-10-06 | 1980-04-15 | Shinetsu Polymer Co | Production of string having core wire |
| JPS5696763A (en) * | 1979-12-28 | 1981-08-05 | Nisso Master Builders Kk | Cement dispersing agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5895634A (en) | 1983-06-07 |
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