CN100567344C - Polymer cement based film water-proof material emulsion and cement composition - Google Patents
Polymer cement based film water-proof material emulsion and cement composition Download PDFInfo
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- CN100567344C CN100567344C CNB2006100998422A CN200610099842A CN100567344C CN 100567344 C CN100567344 C CN 100567344C CN B2006100998422 A CNB2006100998422 A CN B2006100998422A CN 200610099842 A CN200610099842 A CN 200610099842A CN 100567344 C CN100567344 C CN 100567344C
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- emulsion
- proof material
- based film
- film water
- vinyl acetate
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- 239000000839 emulsion Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000004568 cement Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000011414 polymer cement Substances 0.000 title claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000007704 transition Effects 0.000 claims abstract description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000746 allylic group Chemical group 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000005977 Ethylene Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003995 emulsifying agent Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 208000034189 Sclerosis Diseases 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- -1 cyanuric acid alkatriene propyl diester Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PRQREXSTQVWUGV-UHFFFAOYSA-N 6-ethenoxy-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OC=C PRQREXSTQVWUGV-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IYNRVIKPUTZSOR-HWKANZROSA-N ethenyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC=C IYNRVIKPUTZSOR-HWKANZROSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical class CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provide the temperature dependency of the coating strength with good substrate conformability and appropriateness and the elongation of filming smaller, that is to say under low temperature (10 to 5 ℃) or high temperature (28 ℃ to 60 ℃), all have the good elongation of filming, polymer cement based film water-proof material emulsion and cement composition that simultaneously surface viscosity is little.Described polymer cement based film water-proof material contains second-order transition temperature with emulsion and is ethylene-vinyl acetate-multi-functional monomer copolymer and emulsion stabilizer of-9 to+5 ℃, therein ethylene: vinyl acetate: multi-functional monomeric mass ratio is 20～30: 80～70: 0.35～0.8, and emulsion stabilizer only contains polyvinyl alcohol.Described cement composition uses emulsion and cement as essential composition with this polymer cement based film water-proof material.
Description
Technical field
The present invention relates to a kind of polymer cement based film water-proof material emulsion and cement composition.More particularly, relate to smaller polymer cement based film water-proof material emulsion and the cement composition of temperature dependency that the substrate conformability is good, film coated surface viscosity is little, have the coating strength of appropriateness and film and extend.
Background technology
In the past, used the polymer cement composition of synthetic macromolecule emulsions such as adopting acrylic emulsions and vinyl acetate class emulsion to know as water-proof material.
But, owing to these polymer cement compositions can shrink along with the sclerosis of cement, perhaps owing to for example extraneous factors such as motion of temperature variation, freezing fusion and substrate, be easy to generate the such problem in crack after existing in sclerosis, and this fissured generation is the major cause that causes the water-proof material performance impaired, therefore need make improvements.
Therefore, as the emulsion that polymer cement based film water-proof material is used, for example proposed to add high-alumina cement (reference example such as patent documentation 1) in-15 to 15 ℃ the ethylene-vinyl acetate analog copolymer emulsion at the second-order transition temperature (Tg) of multipolymer.But in this case, when Tg was higher than 0 ℃, the low temperature elongation of then filming was poor, otherwise when Tg was lower than 0 ℃, the high temperature elongation of then filming was poor, the shortcoming that therefore exists the temperature dependency of the elongation of filming big, can not average out.
In addition, also proposed to use the polyvinyl alcohol moisture water-based emulsion (reference example such as patent documentation 2) of Tg for-30 ℃ or following ethylene-acrylate-vinyl acetate multipolymer.But, though this emulsion when low temperature, film the elongation good, have the low and big shortcoming of surface viscosity that film of coating strength.
In addition, also proposed to use at Tg and added the emulsion (reference example such as patent documentation 3) that the emulsifying agent be made up of polyvinyl alcohol and nonionic class tensio-active agent obtains in for ethylene-vinyl acetate-multi-functional monomer copolymer emulsion of-30 to-10 ℃.But though the filming elongation of this emulsion when low temperature is good, the coating strength when high temperature is not enough, and, owing to adopt nonionic emulsifying agent, exist by emulsification system and ooze out and cause the big shortcoming of film coated surface viscosity change to the surface as essential composition.
[patent documentation 1] special fair 1-39713 communique
[patent documentation 2] spy opens flat 2-188459 communique
[patent documentation 3] spy opens the 2003-221267 communique
Summary of the invention
As mentioned above, though using polymer cement composition knows as water-proof material, but polymer cement composition in the past is because the motion of temperature variation, freezing, fusion, substrate and the contraction etc. along with the sclerosis of cement composition, produces the crack, produces problems such as surface viscosity and exist in the sclerosis back.
The objective of the invention is to solve the problem that exists in these conventional arts, provide a kind of and have the coating strength of good substrate conformability and appropriateness, the film temperature dependency of elongation is smaller simultaneously, that is to say under low temperature (10 to 5 ℃) or high temperature (28 ℃ to 60 ℃), all to have the little polymer cement based film water-proof material of good film elongation and surface viscosity with emulsion and cement composition.
Inventors of the present invention specialize in for separating time the problems referred to above, found that, contain ethylene-vinyl acetate-multi-functional monomer copolymer and the polymer cement based film water-proof material emulsion of the emulsion stabilizer formed by polyvinyl alcohol by use with particular glass transition temperature and composition, can address the above problem, and can access water-proof material, thereby finish the present invention with premium properties.
That is to say, the invention provides following polymer cement based film water-proof material emulsion and cement composition.
(1), a kind of polymer cement based film water-proof material emulsion, it is to contain second-order transition temperature to be-9 to+5 ℃ the ethylene-vinyl acetate-multi-functional monomer copolymer and the emulsion of emulsion stabilizer, it is characterized in that ethene: vinyl acetate: multi-functional monomeric mass ratio is 20～30: 80～70: 0.035～0.8, and emulsion stabilizer only contains polyvinyl alcohol.
(2), (1) described polymer cement based film water-proof material emulsion, the second-order transition temperature of therein ethylene-vinyl acetate-multi-functional monomer copolymer is-8 to 0 ℃.
(3), (1) or (2) described polymer cement based film water-proof material emulsion, wherein multi-functional act body is multi-functional monomer of esters of acrylic acid and/or the multi-functional monomer of allylic.
(4), 1 to 3 each described polymer cement based film water-proof material emulsion, wherein per 100 mass parts ethylene-vinyl acetates-multi-functional monomer copolymer contain the polyvinyl alcohol of 3～10 mass parts ratios.
(5), with each described polymer cement based film water-proof material in (1) to (4) with emulsion and cement as cement composition that must composition.
According to the present invention, contain ethylene-vinyl acetate-multi-functional monomer copolymer and the polymer cement based film water-proof material emulsion of the emulsion stabilizer formed by polyvinyl alcohol by use with above-mentioned second-order transition temperature and composition, can provide the coating strength that a kind of substrate conformability is good, film coated surface viscosity is little, have appropriateness, polymer cement based film water-proof material emulsion and slob composition that the useless dependency of the temperature of the elongation of filming simultaneously is smaller.
Embodiment
As polymer cement based film water-proof material emulsion of the present invention, use be that second-order transition temperature is ethylene-vinyl acetate-multi-functional monomer copolymer of-9 to+5 ℃.
As the multi-functional monomer that uses in this multipolymer, can enumerate cyanuric acid alkatriene propyl diester, isocyanuric acid triallyl ester, Phthalic acid, diallyl ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, tetramethylolmethane six acrylate, Viscoat 295, methacrylic vinyl acetate, vinyl acrylate, Vinyl crotonate, Sorbic Acid vinyl acetate, hexanedioic acid vinyl ester etc., the multi-functional monomer of preferred acrylate class, the multi-functional monomer of allylic.In addition, multi-functional monomer can use separately, also can two kinds or above use together.
In addition, in the present invention, preferred use 3 functional monomers in the multi-functional monomer.Particularly by using 3 functional monomers, in the time of accessing substrate conformability and low temperature and intensity, all excellent more polymer cement based film water-proof material emulsion of elongation during high temperature.
Polymer cement based film water-proof material of the present invention is essential composition with emulsion with ethylene-vinyl acetate-multi-functional monomer copolymer, but this multipolymer can also be monomeric multipolymers such as further copolymerization (methyl) acrylate, vinyl acetate.Herein, as (methyl) acrylate, can enumerate methyl acrylate, the vinylformic acid ethyl ester, the vinylformic acid isopropyl esters, vinylformic acid n-propyl ester, n-butylacrylate, the vinylformic acid isobutyl, 2-ethylhexyl acrylate, vinylformic acid n-octyl ester, the isooctyl acrylate ester, acrylate such as vinylformic acid nonyl ester, methyl methacrylate, the methacrylic acid n-butyl, the methacrylic acid isobutyl, methacrylic esters such as methacrylic acid 2-(ethyl hexyl) ester, as vinyl ester, can enumerate vinyl acetate, the butyric acid vinyl ester, vinyl propionate base ester, the trimethylacetic acid vinyl ester, the lauric acid vinyl ester, alkyl acid vinyl ester such as tertiary monocarboxylic acid (バ one サ チ Star Network acid) vinyl ester etc.
Monomer beyond these ethene, vinyl acetate and the multi-functional monomer is preferably all accounting for 50 quality % or following in the monomer.
In multipolymer of the present invention, ethene: vinyl acetate: the mass ratio of multi-functional each composition of monomer is 20～30: 80～70: 0.035～0.8, be preferably 22～28: 78～72: 0.1～0.3.By the mass ratio that makes ethene be 20 or more than, can make emulsion have alkali resistance, by be 30 or below, the stable and molecular weight of emulsion state is not reduced.By the mass ratio that makes vinyl acetate be 70 or more than, can access the appropriateness intensity, by be 80 or below, can access the appropriateness elongation.By make multi-functional monomeric mass ratio be 0.035 or more than, can access enough intensity, by be 0.8 or below, can access enough elongations and stable emulsion.
In the present invention, the second-order transition temperature of ethylene-vinyl acetate-multi-functional monomer copolymer (Tg) drops on-9 to+5 ℃ of scopes, is preferably-8 to 0 ℃ of scope.By be+5 ℃ or following, can obtain low temperature elongation and substrate conformability, by be-9 ℃ or more than, can at high temperature obtain enough intensity.
In the present invention, for the emulsifying agent of coating film waterproof material, can use polyvinyl alcohol separately with emulsion.By using polyvinyl alcohol, can prepare by the letex polymerization of routine, and the surface can not adhere to fully as emulsifying agent.Polyvinyl alcohol uses preferably that saponification deg is 88～98, the polymerization degree is 500～3000.In addition, polyvinyl alcohol also can use compound modified through carboxylic acid, sulfonic acid, siloxanes etc. and material that obtain.And, can also adopt the mixture of 2 kinds or above polyvinyl alcohol to adjust the viscosity of emulsion.
The usage quantity of the emulsifying agent of being made up of polyvinyl alcohol, per 100 mass parts ethylene-vinyl acetates-multi-functional monomer copolymer are preferably 3～8 mass parts, more preferably 4～6 mass parts.By be 3 mass parts or more than, can make emulsion state stable, by being 8 mass parts or following, can access the elongation of appropriateness.
Coating film waterproof material of the present invention can also further contain pH regulator agent, tackifier, defoamer, dispersion agent and sanitas etc. as required with in the emulsion.As the pH regulator agent, comprise ammoniacal liquor, 2-amino, 2-methyl, 1-propyl alcohol etc., preferably use non-volatility basifiers such as the 2-amino that with cement mixing the time, do not have volatile matter to emit, 2-methyl, 1-propyl alcohol.As tackifier, can enumerate polyvinyl alcohol, methylcellulose gum, Natvosol, amino formate association type, as defoamer, can enumerate silicone, mineral oils, as dispersion agent, can enumerate polycarboxylic acid class, inorganic Phosphorus etc.
The manufacture method of coating film waterproof material with emulsion had no particular limits, and emulsion polymerisation process can adopt known method.And, polymerizing condition is also had no particular limits, polymerization temperature is 20～80 ℃ usually.As catalyzer, can enumerate persulphate, hydrogen peroxide and various organo-peroxides such as Potassium Persulphate.Under the situation of redox initiation system, can also be used in combination sodium formaldehyde sulphoxylate etc. as reducing substance.
Secondly, cement composition of the present invention uses above-mentioned polymer cement based film water-proof material to use emulsion and cement as essential composition.Hardened gets final product the cement that uses in the said composition so long as can pass through hydration reaction.Cement can use normal portland cement, white portland cement, quick hardening Portland cement, high-alumina cement, slag cement, pulverized fuel ash cement etc., preferably uses high-alumina cement.
The mass ratio of cement and emulsion, with respect to 100 mass parts emulsions, preferred cement is 10～200 mass parts, more preferably the scope of 70～150 mass parts.
In the cement composition of the present invention, can also contain aggregates such as sand, silica sand, silica, titanium dioxide, various reinforcing fibers such as glass fibre, vinylon fiber, mineral fibre, steel fiber, calcium aluminate, the adjustment agent etc. of condensing.
Cement can mix with emulsion when construction, also can sneak in cement in advance after the emulsion of the present invention material in addition, mixes with emulsion when construction.Mixing machine can adopt known devices such as tilting-type mixing machine, V mixing machine and Henschel mixer to carry out.
Embodiment
Below, the present invention will be described in more detail by embodiment, but these embodiment do not constitute any qualification of the present invention.
The performance evaluation of the cement composition that is obtained by following examples and comparative example is carried out as follows.
(1) coating strength and the elongation of filming
Be coated with emulsion on the release paper that is positioned on the plane, dry under 23 ℃, forming thickness is filming of 1mm.After the slaking 14 days, will film and make the drift test sheet with No. 2 dumbbells.Respectively after placing 4 hours under each environment of 0 ℃, 60 ℃ and normal temperature (23 ℃), under identical environment is that 200mm/min, chuck spacing are that the condition of 60mm is measured the coating strength and the elongation of filming with this test film with the draw speed.
(2) surface viscosity
Determine the surperficial adhesion (viscosity) of filming of preparation as stated above with fingers-touch method.
Embodiment 1
Anchor type agitator is being housed, inner capacities is to add 45 mass parts distilled water in 1.5 liters the stainless die autoclave, 35 mass parts vinyl acetates, 1.1 (Japanese kuraray Co., Ltd. makes the mass parts polyvinyl alcohol, " Poval 205 " (Port バ one Le 205), saponification deg is 88 moles of %, mean polymerisation degree is 500), 1.5 (Japanese kuraray Co., Ltd. makes the mass parts polyvinyl alcohol, " Poval 217 " (Port バ one Le 217), saponification deg is 88 moles of %, mean polymerisation degree is 1700) and 0.05 mass parts xitix.With ethene the air in the autoclave is fully taken a breath then.Under agitation in 60 ℃ polymerization temperature with the ethene voltage rise to 5.0MPa, and at the uniform velocity added the hydrogen peroxide of 0.06 mass parts through 8 hours.And, at the uniform velocity added the vinyl acetate of 15 mass parts and the pentaerythritol triacrylate of 0.1 mass parts simultaneously through 6 hours.After beginning to add vinyl acetate, make the ethene voltage rise to 5.7MPa, and keep-up pressure and add to finish up to vinyl acetate into 5.7MPa.Hydrogen peroxide adds and finishes postcooling, adds defoamer, sanitas, mould inhibitor and pH regulator agent, obtains the copolymer emulsion of ethylene-vinyl acetate-pentaerythritol triacrylate.
In the gained emulsion, the content of ethene is 28 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 6000mPas, and pH is 5.0, and second-order transition temperature (Tg) is-5 ℃.Add 17.5 parts of high-alumina cements, No. 7,52.5 parts of silica sands and 10 parts of water in 90 parts of these emulsions, mix by dispersion machine, preparation is as the cement composition of polymer cement based film water-proof material.Make filming of gained cement composition, and under 0～60 ℃ environment, carry out the performance evaluation of cement composition.The result is presented in the table 1.
Reference example 1
In the preparation of ethylene-vinyl acetate-pentaerythritol triacrylate copolymer emulsion, except the quantitative change of polyvinyl alcohol " Poval 205 " is that the quantitative change of 2.0 mass parts, " Poval 217 " is that the quantitative change of 0.5 mass parts, hydrogen peroxide is 0.08 mass parts, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 30 quality %, nonvolatile component 56 quality %, and viscosity is 800mPas, and pH is 5.0, and second-order transition temperature (Tg) is-7 ℃.The evaluation result of cement composition is presented in the table 1.
Reference example 2
In the preparation of ethylene-vinyl acetate-pentaerythritol triacrylate copolymer emulsion, except the quantitative change of hydrogen peroxide is 0.04 mass parts, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 26 quality %, nonvolatile component 56 quality %, and viscosity is 3200mPas, and pH is 5.0, and second-order transition temperature (Tg) is 0 ℃.The evaluation result of cement composition is presented in the table 1.
Comparative example 1
Except when polymerization begins, making the ethene voltage rise to 4.5MPa, remain on 4.5MPa beyond vinyl acetate adds end, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 16 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 3000mPas, and pH is 5.0, and second-order transition temperature (Tg) is 10 ℃.The performance evaluation result of cement composition is presented in the table 1.
Comparative example 2
In the preparation of ethylene-vinyl acetate-pentaerythritol triacrylate copolymer emulsion, except not using pentaerythritol triacrylate, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 28 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 3000mPas, and pH is 5.0, and second-order transition temperature (Tg) is-5 ℃.The performance evaluation result of cement composition is presented in the table 1.
Comparative example 3
Except the usage quantity that makes pentaerythritol triacrylate is 0.01 mass parts, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 28 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 3000mPas, and pH is 5.0, and second-order transition temperature (Tg) is-5 ℃.The Xing Neng Ping valency result of cement composition is presented in the table 1.
Comparative example 4
Except the usage quantity that makes pentaerythritol triacrylate is 0.5 mass parts, carry out similarly to Example 1.
In the gained emulsion, the content of ethene is 28 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 8000mPas, and pH is 5.0, and second-order transition temperature (Tg) is-5 ℃.The performance evaluation result of cement composition is presented in the table 1.
Comparative example 5
Except coupling 0.4 mass parts nonionic emulsifying agent (Kao Corp makes, " emulsifying agent 1150S-70 " (エ マ Le ゲ Application 1150S-70)) as beyond the tensio-active agent that uses in polymerization process, carries out similarly to Example 1.
In the gained emulsion, the content of ethene is 28 quality % in the multipolymer, nonvolatile component 56 quality %, and viscosity is 6000mPas, and pH is 5.0, and second-order transition temperature (Tg) is-6 ℃.The performance evaluation result of cement composition is presented in the table 1.
Table 1
| Embodiment 1 | Reference example 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Copolymer emulsion raw material (mass parts) | ||||||||
| Vinyl acetate | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Pentaerythritol triacrylate | 0.1 | 0.1 | 0.1 | 0.1 | - | 0.01 | 0.5 | 0.1 |
| Emulsifying agent (mass parts) | ||||||||
| Polyvinyl alcohol (Poval 205) | 1.1 | 2.0 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| Polyvinyl alcohol (Poval 217) | 1.5 | 0.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Nonionic emulsifying agent (emulsifying agent 1150S-70) | 0.4 | |||||||
| The composition of copolymer emulsion (mass ratio) | ||||||||
| Ethene | 28 | 30 | 26 | 16 | 28 | 28 | 28 | 28 |
| Vinyl acetate | 71.9 | 69.9 | 73.8 | 83.8 | 72.0 | 71.99 | 71.3 | 71.9 |
| Pentaerythritol triacrylate | 0.14 | 0.14 | 0.15 | 0.17 | - | 0.014 | 0.71 | 0.14 |
| Nonvolatile component (quality %) | 56 | 56 | 56 | 56 | 56 | 56 | 56 | 56 |
| Polyvinyl alcohol content | ||||||||
| (mass parts/copolymer 1 00 mass parts) | 3.74 | 3.49 | 3.84 | 4.36 | 3.75 | 3.75 | 3.70 | 3.74 |
| The physical properties of emulsion | ||||||||
| Viscosity (mPa s) | 6000 | 800 | 3200 | 3000 | 3000 | 3000 | 8000 | 6000 |
| pH | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 |
| Second-order transition temperature (Tg: ℃) | -5 | -7 | 0 | 10 | -5 | -5 | -5 | -6 |
| The physical properties of cement composition | ||||||||
| Coating strength (is placed after 4 hours N/mm 2) | ||||||||
| 0 ℃ (laying temperature) | 8.4 | 7.0 | 9.3 | 14.8 | 8.3 | 8.3 | 10.3 | 5.8 |
| 23℃ | 2.7 | 2.4 | 3.0 | 4.3 | 2.7 | 2.7 | 3.7 | 1.8 |
| 60℃ | 2.0 | 1.5 | 2.3 | 2.0 | 1.5 | 1.7 | 2.6 | 0.6 |
| The elongation of filming (is placed after 4 hours, %) | ||||||||
| 0 ℃ (laying temperature) | 60 | 70 | 50 | 3 | 50 | 47 | 25 | 70 |
| 23℃ | 180 | 200 | 160 | 160 | 220 | 200 | 80 | 240 |
| 60℃ | 120 | 110 | 120 | 100 | 50 | 60 | 50 | 129 |
| Surface adhesion (viscosity) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have |
As shown in table 1, the emulsion that obtains by the embodiment of the invention, coating strength with substrate conformability and appropriateness can be provided, and the temperature dependency of the elongation of filming is smaller, that is to say under low temperature or high temperature, all to have the good elongation of filming, simultaneously the polymer cement based film water-proof material that surface viscosity is little emulsion and cement composition.
On the other hand, in comparative example 1, second-order transition temperature (Tg) reaches 10 ℃ so high, so the substrate poor compliance when low temperature.In comparative example 2, though have the substrate conformability when low temperature, the elongation of filming during high temperature is poor.In comparative example 3, used a spot of multi-functional monomer, though improved the elongation of filming, the elongation and not enough of when high temperature (60 ℃), filming.In comparative example 4, used a large amount of multi-functional monomers, the elongation of filming obviously descends.In comparative example 5, coupling nonionic emulsifying agent as tensio-active agent, though can access enough elongations of filming, coating strength descends under normal temperature and high temperature, and film coated surface produces viscosity.
Claims (5)
1, polymer cement based film water-proof material emulsion, be to contain second-order transition temperature to be-9 to+5 ℃ the ethylene-vinyl acetate-multi-functional monomer copolymer and the emulsion of emulsion stabilizer, it is characterized in that, ethene: vinyl acetate: multi-functional monomeric mass ratio is 22～28: 78～72: 0.1～0.3, wherein multi-functional monomer is multi-functional monomer of esters of acrylic acid and/or the multi-functional monomer of allylic, and emulsion stabilizer only contains polyvinyl alcohol.
2, polymer cement based film water-proof material emulsion according to claim 1, wherein multi-functional monomer is 3 functional monomers.
3, polymer cement based film water-proof material emulsion according to claim 1 and 2, the second-order transition temperature of therein ethylene-vinyl acetate-multi-functional monomer copolymer is-8 to 0 ℃.
4, polymer cement based film water-proof material emulsion according to claim 1 and 2, wherein per 100 mass parts ethylene-vinyl acetates-multi-functional monomer copolymer contain the polyvinyl alcohol of 3～10 mass parts ratios.
5, with each described polymer cement based film water-proof material of claim 1-4 with emulsion and cement as cement composition that must composition.
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| CN102731709B (en) * | 2011-04-07 | 2014-12-24 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion for wallpaper coating and preparation method thereof |
| US9663678B2 (en) | 2012-08-10 | 2017-05-30 | Celanese Sales Germany Gmbh | Waterproofing coating compositions |
| WO2015199984A1 (en) * | 2014-06-25 | 2015-12-30 | Rohm And Haas Company | Emulsion polymer two-component compositions for fast curing cementitious waterproofing membranes |
| CN105130321B (en) * | 2015-07-10 | 2018-05-29 | 昆明风行防水材料有限公司 | A kind of polymer cement waterproof paint that can be used under low temperature environment |
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