JPH0123429B2 - - Google Patents
Info
- Publication number
- JPH0123429B2 JPH0123429B2 JP3321780A JP3321780A JPH0123429B2 JP H0123429 B2 JPH0123429 B2 JP H0123429B2 JP 3321780 A JP3321780 A JP 3321780A JP 3321780 A JP3321780 A JP 3321780A JP H0123429 B2 JPH0123429 B2 JP H0123429B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion
- vinyl acetate
- resin
- copolymer
- chloride
- 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
- 239000000839 emulsion Substances 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 39
- 125000002091 cationic group Chemical group 0.000 claims description 29
- 239000004568 cement Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001449 anionic compounds Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- -1 2-acryloxyethyl Chemical group 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical group Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- GNSQPMMGUIWQJX-UHFFFAOYSA-N 1-chloroethane-1,2-diamine Chemical compound NCC(N)Cl GNSQPMMGUIWQJX-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- ICENLAOCDMWIAT-UHFFFAOYSA-N 2-(dimethylamino)-n-methylprop-2-enamide Chemical compound CNC(=O)C(=C)N(C)C ICENLAOCDMWIAT-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- SCHZETOYDJAZMO-UHFFFAOYSA-M 3-chloropropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCCl SCHZETOYDJAZMO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- LOPVAWVHGAWUPS-UHFFFAOYSA-M [2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl]-trimethylazanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC(O)C[N+](C)(C)C LOPVAWVHGAWUPS-UHFFFAOYSA-M 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 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
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- BGDTWOQNFJNCKH-UHFFFAOYSA-N n-ethyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(CC)CC=C BGDTWOQNFJNCKH-UHFFFAOYSA-N 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- GHVWODLSARFZKM-UHFFFAOYSA-N trimethyl-[3-methyl-3-(prop-2-enoylamino)butyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC(C)(C)NC(=O)C=C GHVWODLSARFZKM-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は特定のカチオン化樹脂が配合された酢
酸ビニル系共重合体エマルジヨンとセメントから
なる改質されたセメント組成物に関する。
酢酸ビニル系共重合体エマルジヨン（VAC系
共重合体エマルジヨンと略記する）は、土木、建
築分野において広く用いられている。即ちコンク
リート建造物の素地表面にモルタルを塗り継ぐ際
の固着剤として、またモルタルを打ち継ぐ際のモ
ルタルへの混和剤として、さらにモルタルと混和
した成型品として用いられており、引張強度、曲
げ強度、圧縮強度、耐衝撃強度、接着強度、耐吸
水性、モルタル流動性等が向上することは広く認
識されている。
VAC系共重合体エマルジヨンには分散安定剤
として種々の水溶性樹脂が用いられたり、保水効
果によるモルタルとの混和安定性向上のために、
水溶性樹脂が用いられている。また種々のノニオ
ン系界面活性剤、アニオン系界面活性剤も乳化剤
として、またエマルジヨン混入モルタルの可使時
間の調整剤として用いられる。
しかし界面活性剤を含んだエマルジヨンを用い
ると、コンクリートの防水性、強度を低下する危
険があつたり、水溶性樹脂を含んだエマルジヨン
を用いると、耐水性が低下する傾向が認められ
る。
しかして本発明者らはこれらの問題を解決すべ
く鋭意検討を加えた結果、特定のカチオン化樹脂
を含んだVAC系共重合体エマルジヨンが、優れ
たセメント組成物を提供することを見い出し、本
発明を完成するいたつた。
本発明によれば、従来のVAC系共重合体エマ
ルジヨンをセメントに混入した場合に比較して、
接着強度、引張強度、耐衝撃強度、耐摩耗性など
の優れたセメント製品を得ることができることに
加えて、曲げ強度、圧縮強度、耐候性、旧コンク
リート素地面への接着性、耐アルカリ性、モルタ
ル混和安定性の優れたセメント組成物を提供する
ことが可能となる。
本発明におけるカチオン化樹脂としては、
一般式
（但し式中R1はアルキレン又はヒドロキシアル
キレン、R2は水素又はアルキル、R3とR4はアル
キル、Ｘは無機アニオンを表わす）で表わされる
カチオン基を含むポリビニルアルコール系樹脂が
あり、これは該カチオン基を有する化合物とポリ
ビニルアルコール系樹脂との反応によつて得られ
る。該化合物を例示すると、３−クロロ−２−ヒ
ドロキシプロピルトリメチルアンモニウムクロラ
イド、３−クロロエチルトリメチルアンモニウム
クロライド、３−クロロプロピルトリメチルアン
モニウムクロライド、３−クロロ−２−ヒドロキ
シエチルトリメチルアンモニウムクロライド、２
−クロロエチレンジアミン、３−クロロ−２−ヒ
ドロキシジメチルアミンなどがあげられる。
カチオン基(b)として一般式
（但し式中R1はアルキレン又はヒドロキシアル
キレン、R2とR5は水素又はアルキル、R3とR4は
アルキル、Ｘは無機アニオン、Ａはアミド窒素又
は酸素）で表わされるカチオン基を有するカチオ
ン化樹脂は、該カチオン基を有する化合物とビニ
ルエステルなかんずく酢酸ビニルとを共重合した
共重合体、及び該共重合体のケン化物である。該
カチオン基を有する化合物としては、Ｎ−アクリ
ルアミドメチルトリメチルアンモニウムクロライ
ド、Ｎ−アクリルアミドエチルトリメチルアンモ
ニウムクロライド、Ｎ−アクリルアミドプロピル
トリメチルアンモニウムクロライド、３−アクリ
ルアミド−３−メチルブチルトリメチルアンモニ
ウムクロライド、２−アクリロキシエチルトリメ
チルアンモニウムクロライド、２−メタクリロキ
シエチルトリメチルアンモニウムクロライド、２
−ヒドロキシ−３−メタクロイルオキシプロピル
トリメチルアンモニウムクロライド、Ｎ−メチル
ジメチルアミノアクリルアミド、ジエチルアミノ
エチルメタクリレートなどがあげられる。
カチオン基(c)として一般式
（但し式中R2とR5は水素又はアルキル、R3とR4
はアルキル、Ｘは無機アニオン、ｎ＝１〜10）で
表わされるカチオン基を有するカチオン化樹脂
は、該カチオン基を有する化合物とビニルエステ
ルなかんずく酢酸ビニルとを共重合した共重合体
及び該共重合体のケン化物である。該カチオン基
を有する化合物としてはアリルトリメチルアンモ
ニウムクロライド、メタアリルトリメチルアンモ
ニウムクロライド、３−ブテントリメチルアンモ
ニウムクロライド、ジメチルアリルアミン、ジメ
チルメタアクリルアミンなどがあげられる。
カチオン基(a)として一般式
（但し式中R2とR5は水素又はアルキル、R3はア
ルキル、Ｘは無機アニオン）で表わされるカチオ
ン基を有するカチオン化樹脂は、該カチオン基を
有する化合物とビニルエステルなかんずく酢酸ビ
ニルとを共重合した共重合体及び該共重合体のケ
ン化物である。該カチオン基を有する化合物とし
ては、ジメチルジアリルアンモニウムクロライ
ド、ジエチルジアリルアンモニウムクロライド、
エチルジアリルアミン、メチルジアリルアミンな
どがあげられる。
また前記化合物とビニルエステルとを共重合す
る際に、ビニルエステルのほかに他の共重合性単
量体を少量併用しうる。
本発明におけるカチオン化樹脂、即ち一般式
(a)、(b)、(c)、(d)で表わされるカチオン基を含むカ
チオン化樹脂のなかで、一般式(a)で表わされるカ
チオン基を含むカチオン化樹脂は、前記のような
カチオン基を有する化合物とポリビニルアルコー
ル系樹脂との付加反応によつて得られるものであ
つて、この反応は苛酷な条件を必要とし、導入さ
れるカチオン基量も限度があり且つ少ない。これ
に対して一般式(b)、(c)、(d)で表わされるカチオン
基を含むカチオン化樹脂は、前記した如くビニル
エステルなかんずく酢酸ビニルと該カチオン基含
有化合物との共重合によつて得た共重合体及び該
共重合体のケン化物であるから、容易にしかも導
入されるカチオン基量も多いものが得られる。従
つて一般式(a)で表わされるカチオン基含有カチオ
ン化樹脂よりも一般式(b)、(c)、(d)で表わされるカ
チオン基含有カチオン化樹脂の方が好適であつて
その使用が望まれる。
本発明における酢酸ビニル系共重合体エマルジ
ヨンとしては、ポリ酢酸ビニルエマルジヨン、酢
酸ビニル−プロピオン酸ビニル共重合体エマルジ
ヨン、酢酸ビニル−バ−サチツク酸ビニル共重合
体エマルジヨンなどの酢酸ビニルと他の脂肪酸ビ
ニルエステルとの共重合体エマルジヨン、酢酸ビ
ニル−アクリル酸エチル共重合体エマルジヨン、
酢酸ビニル−アクリル酸ブチル共重合体エマルジ
ヨン、酢酸ビニル−アクリル酸−２−エチルヘキ
シル共重合体エマルジヨンなどの酢酸ビニルとア
クリル酸エステルとの共重合体エマルジヨン、酢
酸ビニル−エチレン共重合体エマルジヨン、酢酸
ビニル−イソブチレン共重合体エマルジヨンなど
の酢酸ビニルとオレフインとの共重合体、さらに
他のビニル化合物を共重合した多元共重合体エマ
ルジヨンなどがあげられるが、なかでもエチレン
含量が10〜30重量％のエチレン−酢酸ビニル系共
重合体エマルジヨンが、耐アルカリ性、耐久性、
柔軟性、接着性が優れているので好ましいもので
ある。
本発明で用いるカチオン化樹脂のカチオン基含
量は、0.1〜30モル％の範囲が適当であり、0.1モ
ル％未満では効果に乏しく、30モル％を越えるも
のは得がたいので、0.1〜30モル％のカチオン基
含有カチオン化樹脂から適宜選択して用いること
が望ましい。
カチオン化樹脂の使用時期はVAC系共重合体
エマルジヨンを乳化重合によつて製造する際の乳
化剤として用いてもよく、またポリビニルアルコ
ール、メチルセルロースなどの保護コロイド、ノ
ニオン界面活性剤を用いて得られた該エマルジヨ
ンに後添加してもよく、さらに粉末のVAC系共
重合体を再乳化する時に添加してもよい。
VAC系共重合体エマルジヨンを乳化重合する
際の乳化剤として用いる場合のカチオン化樹脂の
量は、カチオン基の種類、カチオン基含量によつ
ても異なるが、おおよそ全系に対して0.1〜10重
量％の範囲から適宜適量を選択することが望まし
く、エマルジヨンに後添加する場合には樹脂固形
分50重量％のエマルジヨンを基準として１〜10重
量％が適当である。
カチオン化樹脂を乳化剤として前記酢酸ビニル
系共重合体エマルジヨンを得る場合は、通常の乳
化重合方法に従つて行えばよく、重合触媒として
はレドツクス触媒があげられる。即ち酸化剤また
は開始剤としては過酸化水素、有機過酸化物（ベ
ンゾイルパーオキサイド、ラウロイルパーオキサ
イド、ｔ−ブチルハイドロパーオキサイドなど）、
過硫酸アンモニウム、過硫酸カリウム、還元剤ま
たは活性剤としては重亜硫酸塩、硫酸第一鉄、ナ
トリウムホルムアルデヒド、亜鉛ホルムアルデヒ
ドスルフオキシレートなどがあげられる。さらに
好ましい触媒として２，2′−アゾビス−（２−ア
ミジノプロパン）塩酸塩があげられる。
本発明における酢酸ビニル系共重合体エマルジ
ヨン、なかんずくエチレン−酢酸ビニル系共重合
体エマルジヨンのセメントに対する配合量は、セ
メントに対して樹脂固形分として２〜2500重量％
であるが、左官モルタル、下地調整材、補修材、
コンクリート、吹付材、ノロなどの用途の場合は
セメントに対して樹脂固形分として２〜100重量
％、好ましくは５〜20重量％、防水材、注入材、
接着剤などの用途の場合は20〜2500重量％、好ま
しくは50〜500重量％である。
またセメントのほかに砂、小石、枠石などの各
種骨材を配合してもよい。
次に実施例によつて本発明を具体的に説明す
る。尚例中「部」、「％」とあるのはことわりのな
い限り重量基準である。
(1) エチレン−酢酸ビニル系共重合体エマルジヨ
ンの製造
実施例 １
酢酸ビニル111部、水155部、３−クロロ−２−
ヒドロキシプロピルトリメチルアンモニウムクロ
ライドとポリビニルアルコール（平均重合度
1800、ケン化度98モル％）とを反応して得られた
カチオン化度（カチオン化樹脂中のカチオン基量
をモル％で表示）3.2モル％のカチオン化樹脂９
部、炭酸ナトリウム0.09部をオートクレーブに仕
込み、撹拌しながら温度60℃に昇温し、50Kg／cm2
になるまでエチレンを圧入した。エチレン圧を50
Kg／cm2に保持しながら、酒石酸／過酸化水素を添
加して重合を開始させた。残留モノマーが約0.5
％以下になるまで重合した後冷却してエマルジヨ
ンを得た。エチレン含有量は16％、樹脂固形分は
54.7％であつた。得られたエマルジヨンをEVA
−Ａとする。
実施例 ２
酢酸ビニル125部、水150部、酢酸ビニルとアリ
ルトリメチルアンモニウムクロライドとの共重合
体ケン化物であるカチオン化度1.1モル％のカチ
オン化樹脂（ケン化度87モル％）7.5部、第２リ
ン酸ソーダ0.9部をオートクレーブに仕込み、撹
拌しながら温度70℃に昇温し、50Kg／cm2になるま
でエチレンを圧入した。エチレン圧を50Kg／cm2に
保持しながら、温硫酸カリウムを添加して重合を
開始させた。残留モノマーが約0.5％以下になる
まで重合した後、冷却してエマルジヨンを得た。
エチレン含有量は17％、樹脂固形分は55.1％であ
つた。得られたエマルジヨンをEVA−Ｂとする。
実施例 ３
酢酸ビニル120部、水150部、酢酸ビニルとＮ−
アクリルアミドプロピル−３−トリメチルアンモ
ニウムクロライドとの共重合体ケン化物であるカ
チオン化度5.5モル％のカチオン化樹脂（ケン化
度89モル％）６部、をオートクレーブに仕込み、
撹拌しながら温度70℃に昇温し、50Kg／cm2になる
までエチレンを圧入した。エチレン圧を50Kg／cm2
に保持しながら、２，2′−アゾビス−（２−アミ
ジノプロパン）塩酸塩を添加して重合を開始させ
た。残留モノマーが約0.5％以下になるまで重合
した後、冷却してエマルジヨンを得た。エチレン
含有量は18％、樹脂固形分は53.8％であつた。得
られたエマルジヨンをEVA−Ｃとする。
実施例 ４
実施例３におけるカチオン化樹脂に替えて酢酸
ビニルとジメチルジアリルアンモニウムクロライ
ドとの共重合体であるカチオン化度４モル％のカ
チオン化樹脂を用いたほかは同様にして、エチレ
ン含有量18％、樹脂固形分55.2％のエマルジヨン
を得た。得られたエマルジヨンをEVA−Ｄとす
る。
実施例 ５
実施例４におけるカチオン化樹脂に替えて酢酸
ビニルとアリルトリメチルアンモニウムクロライ
ドとＮ−アクリルアミドエチルトリメチルアンモ
ニウムクロライドとの共重合体ケン化物であるカ
チオン化度2.4モル％のカチオン化樹脂（ケン化
物85モル％）を用いたほかは同様にして、エチレ
ン含有量18％、樹脂固形分54.9％のエマルジヨン
を得た。得られたエマルジヨンをEVA−Ｅとす
る。
対照例 １
実施例２において使用したカチオン化樹脂に替
えて、ポリビニルアルコール（重合度1700、ケン
化物88モル％）を6.5部用いたほかは同様にして、
エマルジヨンを得た。エチレン含有量は17％、樹
脂固形分は55％であつた。得られたエマルジヨン
をEVA−ａとする。
対照例 ２
実施例２において使用したカチオン化樹脂に替
えて、ノニオン界面活性剤であるポリオキシエチ
レンノニルフエニルエーテル6.5部用いたほかは
同様にして、エマルジヨンを得た。エチレン含有
量は17％、樹脂固形分は54.5％であつた。得られ
たエマルジヨンをEVA−ｂとする。
(2) エマルジヨン混入モルタルの製造及びその諸
特性セメント混和用ポリマーデイスパージヨン
（JIS−A6203）に準じて、セメント100部、豊
浦標準砂300部、にEVAエマルジヨンである
EVA−Ａ〜Ｄ及びEVA−ａ、EVA−ｂを夫々
樹脂固形分換算で10部および適量の水を混練
し、28日間養生した後得られたセメントモルタ
ル試験片の各特性値を測定し、第１表に記載し
た。また対照例３としてEVAエマルジヨンを
用いないセメントモルタルの各特性値を求め、
第１表に記載した。
実施例６〜７及び対照例４
実施例６ではEVA−Ａの樹脂固形分100重量部
に対してセメントを40部の割合で混合撹拌した
後、約２mm厚のシート状に流延し20℃×65％RH
の雰囲気下で６週間養生後機械的性質を測定し
た。実施例７では実施例６のEVA−Ａに替えて
EVA−Ｂを用いたほかは、実施例６と同様にし
てシートを得て、その機械的性質を測定した。対
照例４では実施例６のEVA−Ａに替えてEVA−
ａを用いた場合である。結果を第２表にまとめて
示した。
The present invention relates to a modified cement composition comprising cement and a vinyl acetate copolymer emulsion blended with a specific cationized resin. Vinyl acetate copolymer emulsion (abbreviated as VAC copolymer emulsion) is widely used in the civil engineering and construction fields. In other words, it is used as a fixing agent when applying mortar to the surface of a concrete building, as an admixture to mortar when applying mortar, and as a molded product mixed with mortar. It is widely recognized that compressive strength, impact strength, adhesive strength, water absorption resistance, mortar fluidity, etc. are improved. Various water-soluble resins are used as dispersion stabilizers in VAC copolymer emulsions, and in order to improve the stability of mixing with mortar due to their water retention effect,
A water-soluble resin is used. Various nonionic surfactants and anionic surfactants are also used as emulsifiers and as pot life adjusters for mortar mixed with emulsion. However, if an emulsion containing a surfactant is used, there is a risk of reducing the waterproof properties and strength of the concrete, and if an emulsion containing a water-soluble resin is used, there is a tendency for the water resistance to decrease. However, as a result of intensive studies to solve these problems, the present inventors discovered that a VAC copolymer emulsion containing a specific cationized resin provides an excellent cement composition. Itatsuta completes his invention. According to the present invention, compared to the case where a conventional VAC copolymer emulsion is mixed into cement,
In addition to being able to obtain cement products with excellent adhesive strength, tensile strength, impact strength, abrasion resistance, etc., we can also obtain cement products with excellent flexural strength, compressive strength, weather resistance, adhesion to old concrete surfaces, alkali resistance, and mortar. It becomes possible to provide a cement composition with excellent mixing stability. The cationized resin in the present invention has the general formula There is a polyvinyl alcohol resin containing a cationic group represented by the formula (wherein R 1 is alkylene or hydroxyalkylene, R 2 is hydrogen or alkyl, R 3 and R 4 are alkyl, and X is an inorganic anion). It is obtained by reacting a compound having the cationic group with a polyvinyl alcohol resin. Examples of the compounds include 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloroethyltrimethylammonium chloride, 3-chloropropyltrimethylammonium chloride, 3-chloro-2-hydroxyethyltrimethylammonium chloride, 2
-chloroethylenediamine, 3-chloro-2-hydroxydimethylamine, and the like. General formula for cationic group (b) (wherein R 1 is alkylene or hydroxyalkylene, R 2 and R 5 are hydrogen or alkyl, R 3 and R 4 are alkyl, X is an inorganic anion, and A is amide nitrogen or oxygen). The polymerized resin is a copolymer obtained by copolymerizing the compound having the cationic group and a vinyl ester, especially vinyl acetate, and a saponified product of the copolymer. Examples of compounds having the cationic group include N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 3-acrylamido-3-methylbutyltrimethylammonium chloride, and 2-acryloxyethyl. Trimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2
-Hydroxy-3-methacroyloxypropyltrimethylammonium chloride, N-methyldimethylaminoacrylamide, diethylaminoethyl methacrylate, and the like. General formula for cationic group (c) (However, in the formula, R 2 and R 5 are hydrogen or alkyl, R 3 and R 4
is an alkyl, X is an inorganic anion, and the cationized resin having a cationic group represented by n=1 to 10) is a copolymer obtained by copolymerizing a compound having the cationic group with a vinyl ester, particularly vinyl acetate, and a copolymer of the copolymer. It is a saponified product of union. Examples of the compound having the cationic group include allyltrimethylammonium chloride, methalyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethylallylamine, and dimethylmethacrylamine. General formula as cationic group (a) (However, in the formula, R 2 and R 5 are hydrogen or alkyl, R 3 is alkyl, and X is an inorganic anion). These are a copolymerized copolymer and a saponified product of the copolymer. Examples of the compound having the cationic group include dimethyldiallylammonium chloride, diethyldiallylammonium chloride,
Examples include ethyl diallylamine and methyl diallylamine. Further, when copolymerizing the above compound and vinyl ester, a small amount of other copolymerizable monomers may be used in combination with the vinyl ester. The cationized resin in the present invention, that is, the general formula
Among the cationized resins containing the cationic groups represented by (a), (b), (c), and (d), the cationic resins containing the cationic group represented by the general formula (a) are as follows. It is obtained by an addition reaction between a compound having a cationic group and a polyvinyl alcohol resin, and this reaction requires harsh conditions, and the amount of cationic groups introduced is limited and small. On the other hand, cationized resins containing cationic groups represented by general formulas (b), (c), and (d) are produced by copolymerizing vinyl esters, especially vinyl acetate, with the cationic group-containing compound, as described above. Since the obtained copolymer and the saponified product of the copolymer are used, it is easy to obtain a product with a large amount of cationic groups introduced. Therefore, the cationic resins containing cationic groups represented by the general formulas (b), (c), and (d) are more suitable than the cationic resins containing the cationic groups represented by the general formula (a), and their use is desired. Examples of the vinyl acetate copolymer emulsion in the present invention include polyvinyl acetate emulsion, vinyl acetate-vinyl propionate copolymer emulsion, and vinyl acetate-vinyl versatate copolymer emulsion containing vinyl acetate and other fatty acids. Copolymer emulsion with vinyl ester, vinyl acetate-ethyl acrylate copolymer emulsion,
Copolymer emulsion of vinyl acetate and acrylic acid ester such as vinyl acetate-butyl acrylate copolymer emulsion, vinyl acetate-2-ethylhexyl acrylate copolymer emulsion, vinyl acetate-ethylene copolymer emulsion, vinyl acetate - Copolymers of vinyl acetate and olefin such as isobutylene copolymer emulsions, and multi-component copolymer emulsions copolymerized with other vinyl compounds, among others, ethylene with an ethylene content of 10 to 30% by weight. -Vinyl acetate copolymer emulsion has alkali resistance, durability,
It is preferable because it has excellent flexibility and adhesiveness. The cationic group content of the cationized resin used in the present invention is suitably in the range of 0.1 to 30 mol%; if it is less than 0.1 mol%, the effect is poor, and if it exceeds 30 mol%, it is difficult to obtain. It is desirable to appropriately select and use cationized resins containing cationic groups. The cationized resin can be used as an emulsifier when producing a VAC copolymer emulsion by emulsion polymerization, or it can be used as an emulsifier when producing a VAC copolymer emulsion by emulsion polymerization. It may be added later to the emulsion, or may be added when re-emulsifying the powdered VAC copolymer. When using a VAC copolymer emulsion as an emulsifier in emulsion polymerization, the amount of cationized resin varies depending on the type of cationic group and the cationic group content, but is approximately 0.1 to 10% by weight based on the total system. It is desirable to select an appropriate amount from the range of 1 to 10% by weight, based on the emulsion with a resin solid content of 50% by weight, when it is post-added to the emulsion. When the vinyl acetate copolymer emulsion is obtained using a cationized resin as an emulsifier, a conventional emulsion polymerization method may be followed, and a redox catalyst may be used as the polymerization catalyst. That is, as the oxidizing agent or initiator, hydrogen peroxide, organic peroxides (benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, etc.),
Ammonium persulfate, potassium persulfate, reducing agents or activators include bisulfite, ferrous sulfate, sodium formaldehyde, zinc formaldehyde sulfoxylate, and the like. A more preferred catalyst is 2,2'-azobis-(2-amidinopropane) hydrochloride. In the present invention, the blending amount of the vinyl acetate copolymer emulsion, especially the ethylene-vinyl acetate copolymer emulsion, in the cement is 2 to 2500% by weight as resin solid content based on the cement.
However, plastering mortar, ground preparation materials, repair materials,
For applications such as concrete, spraying materials, and slag, the resin solid content is 2 to 100% by weight, preferably 5 to 20% by weight, based on cement, waterproofing materials, injection materials,
For applications such as adhesives, the amount is 20 to 2500% by weight, preferably 50 to 500% by weight. In addition to cement, various aggregates such as sand, pebbles, and stones may be mixed. Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. (1) Production example of ethylene-vinyl acetate copolymer emulsion 1 111 parts of vinyl acetate, 155 parts of water, 3-chloro-2-
Hydroxypropyltrimethylammonium chloride and polyvinyl alcohol (average degree of polymerization
Cationized resin 9 with a degree of cationization (the amount of cationic groups in the cationized resin is expressed in mol%) of 3.2 mol% obtained by reacting with 1800, saponification degree of 98 mol%)
1 part and 0.09 part of sodium carbonate were charged into an autoclave, and the temperature was raised to 60℃ while stirring, and 50Kg/cm 2
Ethylene was injected until the 50 ethylene pressure
Polymerization was initiated by addition of tartaric acid/hydrogen peroxide while maintaining at Kg/cm 2 . Residual monomer is approximately 0.5
% or less, and then cooled to obtain an emulsion. Ethylene content is 16%, resin solid content is
It was 54.7%. EVA the obtained emulsion
-A. Example 2 125 parts of vinyl acetate, 150 parts of water, 7.5 parts of a cationized resin with a cationization degree of 1.1 mol% (saponification degree of 87 mol%), which is a saponified copolymer of vinyl acetate and allyltrimethylammonium chloride, 0.9 part of sodium diphosphate was charged into an autoclave, and the temperature was raised to 70° C. while stirring, and ethylene was pressurized until the temperature reached 50 kg/cm 2 . While maintaining the ethylene pressure at 50 Kg/cm 2 , warm potassium sulfate was added to initiate polymerization. After polymerization until the residual monomer amount was about 0.5% or less, it was cooled to obtain an emulsion.
The ethylene content was 17% and the resin solids content was 55.1%. The obtained emulsion is designated as EVA-B. Example 3 120 parts of vinyl acetate, 150 parts of water, vinyl acetate and N-
Charge 6 parts of a cationized resin with a cationization degree of 5.5 mol% (saponification degree of 89 mol%), which is a saponified copolymer with acrylamide propyl-3-trimethylammonium chloride, into an autoclave.
The temperature was raised to 70° C. while stirring, and ethylene was pressurized until the amount reached 50 kg/cm 2 . Ethylene pressure 50Kg/cm 2
2,2'-azobis-(2-amidinopropane) hydrochloride was added to initiate polymerization while maintaining the temperature. After polymerization until the residual monomer content was reduced to about 0.5% or less, it was cooled to obtain an emulsion. The ethylene content was 18% and the resin solids content was 53.8%. The obtained emulsion is designated as EVA-C. Example 4 The same procedure was carried out except that a cationized resin having a degree of cationization of 4 mol%, which is a copolymer of vinyl acetate and dimethyl diallylammonium chloride, was used instead of the cationized resin in Example 3, but the ethylene content was 18 %, and an emulsion with a resin solid content of 55.2% was obtained. The obtained emulsion is referred to as EVA-D. Example 5 In place of the cationized resin in Example 4, a cationized resin (saponified product) with a degree of cationization of 2.4 mol%, which is a saponified copolymer of vinyl acetate, allyltrimethylammonium chloride, and N-acrylamidoethyltrimethylammonium chloride, was used. An emulsion with an ethylene content of 18% and a resin solid content of 54.9% was obtained in the same manner except that 85 mol %) was used. The obtained emulsion is designated as EVA-E. Control Example 1 The same procedure was carried out except that 6.5 parts of polyvinyl alcohol (degree of polymerization 1700, saponified product 88 mol%) was used instead of the cationized resin used in Example 2.
I got an emulsion. The ethylene content was 17% and the resin solids content was 55%. The obtained emulsion is referred to as EVA-a. Control Example 2 An emulsion was obtained in the same manner as in Example 2, except that 6.5 parts of polyoxyethylene nonyl phenyl ether, which is a nonionic surfactant, was used in place of the cationized resin used in Example 2. The ethylene content was 17% and the resin solids content was 54.5%. The obtained emulsion is designated as EVA-b. (2) Manufacture of emulsion-mixed mortar and its characteristics In accordance with polymer dispersion for cement mixing (JIS-A6203), EVA emulsion is mixed with 100 parts of cement and 300 parts of Toyoura standard sand.
EVA-A to D, EVA-a, and EVA-b were each kneaded with 10 parts in terms of resin solid content and an appropriate amount of water, and after curing for 28 days, each characteristic value of the obtained cement mortar test piece was measured, It is listed in Table 1. In addition, as a control example 3, each characteristic value of cement mortar without EVA emulsion was determined.
It is listed in Table 1. Examples 6 to 7 and Comparative Example 4 In Example 6, cement was mixed and stirred at a ratio of 40 parts by weight to 100 parts by weight of resin solid content of EVA-A, and then cast into a sheet with a thickness of about 2 mm and heated at 20°C. ×65%RH
The mechanical properties were measured after curing for 6 weeks in an atmosphere of In Example 7, instead of EVA-A in Example 6,
A sheet was obtained in the same manner as in Example 6 except that EVA-B was used, and its mechanical properties were measured. In Control Example 4, EVA-A was used in place of EVA-A in Example 6.
This is the case when a is used. The results are summarized in Table 2.
【表】【table】
【表】【table】
Claims (1)
トに対して樹脂固形分として２〜2500重量％の割
合で混入してなるセメント組成物において、 一般式 （但し式中R1はアルキレン又はヒドロキシアル
キレン、R2とR5は水素又はアルキル、R3とR4は
アルキル、Ｘは無機アニオン、Ａはアミド窒素又
は酸素を表わす）で表わされるカチオン基の群
(a)、(b)、(c)、(d)から選ばれた１種又は２種以上の
カチオン基を含有するカチオン化樹脂を配合した
酢酸ビニル系共重合体エマルジヨンを用いること
を特徴とする改質されたセメント組成物。[Scope of Claims] 1. A cement composition comprising a vinyl acetate copolymer emulsion mixed with the cement at a ratio of 2 to 2500% by weight as a resin solid content, (wherein R 1 is alkylene or hydroxyalkylene, R 2 and R 5 are hydrogen or alkyl, R 3 and R 4 are alkyl, X is an inorganic anion, and A is amide nitrogen or oxygen). group
It is characterized by using a vinyl acetate copolymer emulsion blended with a cationized resin containing one or more cationic groups selected from (a), (b), (c), and (d). modified cement composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3321780A JPS56129654A (en) | 1980-03-14 | 1980-03-14 | Reformed cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3321780A JPS56129654A (en) | 1980-03-14 | 1980-03-14 | Reformed cement composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56129654A JPS56129654A (en) | 1981-10-09 |
| JPH0123429B2 true JPH0123429B2 (en) | 1989-05-02 |
Family
ID=12380273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3321780A Granted JPS56129654A (en) | 1980-03-14 | 1980-03-14 | Reformed cement composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56129654A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013221033A (en) * | 2012-04-12 | 2013-10-28 | Shikoku Chem Corp | Water-based coating material composition and wall surface decoration method |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57166351A (en) * | 1981-03-31 | 1982-10-13 | Kuraray Co | Cement composition |
| JPS5832050A (en) * | 1981-08-20 | 1983-02-24 | 株式会社クラレ | Aqueous dispersion for cement admixture |
| JPS5869764A (en) * | 1981-10-15 | 1983-04-26 | 株式会社クラレ | Admixing agent for cement |
| JPS62187187A (en) * | 1986-02-12 | 1987-08-15 | 株式会社 オ−トセツト | Resilient surface layer material |
| JP4976028B2 (en) * | 2006-03-07 | 2012-07-18 | 日本合成化学工業株式会社 | Cement admixture |
| JP4997489B2 (en) * | 2007-08-07 | 2012-08-08 | 日本合成化学工業株式会社 | Cement mortar admixture |
-
1980
- 1980-03-14 JP JP3321780A patent/JPS56129654A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013221033A (en) * | 2012-04-12 | 2013-10-28 | Shikoku Chem Corp | Water-based coating material composition and wall surface decoration method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56129654A (en) | 1981-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8461247B2 (en) | Dispersion compositions for tile adhesives | |
| US5069721A (en) | Mortar concrete composition | |
| US20100240819A1 (en) | Copolymer mixture | |
| KR102404115B1 (en) | Chloroprene-based polymer latex composition, mixed latex composition using the composition, and uses thereof | |
| EP0256144B1 (en) | Alkaline curing emulsions for use in cement admixtures | |
| JPH0123429B2 (en) | ||
| US3360493A (en) | Hydraulic cement compositions and methods | |
| JP3281079B2 (en) | Polymer cement composition | |
| JP2886662B2 (en) | Polymer cement mortar composition | |
| JPS6221375B2 (en) | ||
| JPH0699172B2 (en) | Cement composition | |
| JP3094551B2 (en) | Composition for cement | |
| JP3342525B2 (en) | Cement dispersant composition | |
| JP4428148B2 (en) | Polymer cement composition | |
| US6262163B1 (en) | Process for preparing protective-colloid-stabilized vinyl ester or vinyl ester-ethylene polymers in the form of their aqueous dispersions | |
| JPH0226855A (en) | Cement composition | |
| JPS6172662A (en) | Composition for cement | |
| JPS6283346A (en) | Composition for cement | |
| JPS5869763A (en) | Reform of cementitious mortar adhesion | |
| JPS6339026B2 (en) | ||
| JPS5815569A (en) | Rust prevention of iron surface | |
| JPH10139514A (en) | Polymer-cement composition | |
| JPS6143303B2 (en) | ||
| JPH0146469B2 (en) | ||
| JPS5914416B2 (en) | Composition for mixing cement |