JPH0346417B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an ethylene-vinyl acetate copolymer emulsion and cement, which contain a water-soluble resin and a specific cationic surfactant, and in which the water-soluble resin and the specific cationic surfactant are post-added to the emulsion. The present invention relates to a cement composition comprising the following, and a cement composition comprising an aggregate and a filler added thereto. Cement compositions in which ethylene-vinyl acetate copolymer emulsion (hereinafter abbreviated as EVA emulsion) is blended with cement, as well as aggregates and fillers, can be hydraulically hardened by adding an appropriate amount of water. Cement products with outstanding mechanical strength such as bending strength, tensile adhesive strength, and compressive strength can be obtained not only during dry curing but also when cured in water, as well as impact resistance, abrasion resistance, and adhesion to old concrete surfaces. It is also known to have excellent weather resistance. However, as a result of extensive research in order to further improve the above-mentioned excellent properties, the present inventors discovered that the present invention contains both a water-soluble resin and a specific cationic surfactant.
In addition, by using an EVA emulsion in which a water-soluble resin and the specific cationic surfactant are added to the emulsion afterward, a cement compound, a compound containing aggregate and filler in addition to cement, can be prepared as described above. It was discovered for the first time that the various properties, particularly the tensile adhesive strength and the adhesion to the substrate, were even more excellent, leading to the completion of the present invention. That is, the present invention comprises (A) a water-soluble resin and (B) a cationic surfactant selected from at least one of long-chain alkyltrimethylammonium chloride and long-chain alkylbenzylmethylammonium chloride, and (A) This is a cement composition prepared by blending an ethylene-vinyl acetate copolymer emulsion obtained by post-adding components and component (B) to the emulsion, and cement or further aggregate and/or filler. The present invention is characterized in that the EVA emulsion contains (A) a water-soluble resin and (B) a specific cationic surfactant, and that both components (A) and (B) are post-added to the emulsion. By such treatment, the tensile adhesive strength of the emulsion-cement composition can be significantly improved. In the present invention, the emulsion contains (A) a water-soluble resin and (B) a specific cationic surfactant, and (A) the water-soluble resin and (B) the specific cationic surfactant are post-added to the emulsion. The EVA emulsion is
It includes the following aspects. (1) When producing EVA emulsion by emulsion polymerization in an aqueous medium using ethylene and vinyl acetate or other copolymerizable monomers as necessary,
(A) water-soluble resin is used as a protective colloid, and (A) water-soluble resin and (B) are added to the obtained EVA emulsion.
Contains cationic surfactant. (2) An EVA emulsion obtained by using a surfactant as an emulsifier when producing an EVA emulsion, and (A) a water-soluble resin and (B) a cationic surfactant mixed therein. (3) An EVA emulsion that does not contain (A) a water-soluble resin and (B) a cationic surfactant is blended with (A) a water-soluble resin and (B) a cationic surfactant. In any of the above embodiments, it is not necessary to use predetermined amounts of (A) water-soluble resin and (B) cationic surfactant from the beginning, and it is sufficient to add them sequentially depending on the purpose. However, it is not limited to the embodiments (1) to (3), and cement, aggregate,
At the time of blending with filler, (A) water-soluble resin and (B) cationic surfactant are added in amounts suitable for the purpose and use.
There is no problem as long as it is included in the EVA emulsion, but among the above embodiments, embodiment (1) is preferred. The amounts of (A) water-soluble resin and (B) cationic surfactant in the EVA emulsion at the time of use are EVA emulsion 100 with a resin solid content of 50% by weight.
(A) 0.1 to 6 parts by weight of water-soluble resin, (B)
A range of 0.1 to 5 parts by weight of the cationic surfactant is suitable. (A) When using a water-soluble resin as a protective colloid during the production of EVA emulsion, the appropriate amount is 0.1 to 6% by weight based on the total monomer amount including vinyl acetate or other copolymers. be. (B) When using a cationic surfactant as an emulsifier during the production of EVA emulsion, it should be in the range of 0.1 to 2% by weight based on the total amount of vinyl acetate or the total amount of monomers including copolymerizable monomers. Appropriate.
The method for producing EVA emulsion by emulsion polymerization does not require any special method, and may be carried out based on a known emulsion polymerization method. In addition, it is easier to obtain a stable emulsion by using a known anionic surfactant or nonionic surfactant in an emulsion containing (A) a water-soluble resin and (B) a cationic surfactant. preferable. The (A) water-soluble resin in the present invention includes polyvinyl alcohol, partially saponified polyvinyl alcohol, derivatives of polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, sodium polyacrylate, Examples include polyacrylic acid amide,
These may be used alone or in combination, but (partially saponified) polyvinyl alcohol is preferred. (B) As the cationic surfactant, long-chain alkyltrimethylammonium chloride such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and laurylbenzylmethylammonium chloride,
These are long-chain alkylbenzylmethylammonium chlorides such as stearylbenzyldimethylammonium chloride, and one or more of these are used in combination. Examples of anionic surfactants include higher alcohol sulfate ester salts, alkylbenzene sulfonates, polyoxyethylene alkylphenol sulfate salts, polyoxyethylene alkyl sulfate salts, dialkyl sulfosuccinates, etc. Nonionic surfactants include teeth,
polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, oxyethylene-oxypropyl block copolymer,
Examples include polyoxyethylene sorbitan monolaurate. The ethylene content of the EVA emulsion in the present invention is suitably in the range of 10 to 30% by weight. Components other than ethylene and vinyl acetate include unsaturated vinyl monomers having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate, N
- unsaturated vinyl monomers having N-methylol groups or alkoxy groups, such as methylol compounds such as methylol acrylamide, N-methylol methacrylamide and their alkyl ethers of methyl, ethyl and butyl ethers, acrylic acid, icotanoic acid, maleic acid and Unsaturated vinyl monomers having a carboxy group or carboxylic acid ester group such as those esters, dimethylaminoethyl acrylate, diethylaminoethyl acrylate,
A small amount of cationic monomers such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, and triethylaminoacetic acid vinyl halide salt can be used. The mixing ratio of EVA emulsion and cement varies depending on the purpose and use, but it can be used for cement filters, mortar for recoating, concrete construction, blocks, bails, mortar, mortar for slate pavement, mortar lining board, anticorrosion lining material, etc. When used as a deck covering material, etc., EVA emulsion is applied to cement based on the resin solid content.
A suitable proportion is 2 to 50 parts by weight per 100 parts by weight. In this case, the appropriate ratio of aggregate to cement is in the range of aggregate/cement=0/1 to 6/1 (weight ratio). Further, when a filler is used, a range of filler/cement=3/1 to 1/1 (weight ratio) is suitable. In addition, when used in caulking agents, joint fillers, waterproofing agents, cushioning binders for all-weather coats, spraying agents, waterproof sheets, protective sheets, etc., use an EVA emulsion of 15% by weight per 100 parts by weight of cement based on resin solid content. A proportion of ~500 parts by weight is suitable. In this case, the ratio of aggregate and cement is aggregate/cement = 0.5/1 to 2/1 (weight ratio)
A range of is appropriate. In addition, when using a filler, filler/cement = 0.5/1 to 2/1 (parts by weight)
A range of is appropriate. The cement used in the present invention includes:
Examples include portland cement, alumina cement, ultra early strength cement, early strength cement, blast furnace cement, fly ash, and other known materials. As aggregates, sand, crushed stone, pebbles,
Examples include kansuishi, vermiculite, limestone, silica sand, and asbestos. Examples of fillers include calcium carbonate, titanium oxide, talc, magnesium hydroxide, aluminum hydroxide, carbon black, barium sulfate, clay, and bentonite. In addition, the EVA emulsion in the present invention includes:
Glycols, antifoaming agents, preservatives, anti-bacterial agents, coloring agents, solvents, dispersants, wetting agents, penetrating agents, etc. may be added in appropriate amounts to adjust workability, stability, and the like. Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" and "%" are based on weight unless otherwise specified. Example 1 Emulsion polymerization was carried out using ethylene, vinyl acetate, a catalyst (diacetyl peroxide), polyvinyl alcohol, and a nonionic surfactant (polyoxyethylene nonyl phenyl ether), and the ethylene content was 17.5.
%, and an EVA emulsion with a resin solid content of 55% was obtained.
Polyvinyl alcohol and a cationic surfactant (stearylbenzyldimethylammonium chloride) were added to this emulsion to obtain an emulsion containing 3.5% and 0.5% of polyvinyl alcohol and cationic surfactant, respectively, based on the emulsion. This emulsion is referred to as EVA-1. According to the Polymer Dice Version for Cement Mixing (JIS-A6203), 100 parts of cement, 300 parts of Toyoura standard sand, 10 parts of EVA-1 as a resin solid content, and an appropriate amount of water were mixed, and the mixture was cured for 28 days. The characteristic values of the cement mortar specimens were measured.
It is listed in Table 1. Also, the resin solid content of EVA-1
100 parts by weight of cement, 6 parts of aggregate (silica sand)
No.) 200 parts were mixed and stirred to form a sheet approximately 2 mm thick. This sheet was flexible and had excellent water impermeability, making it suitable for use as a protective sheet or a waterproof sheet. Example 2 Anionic surfactant (sodium dodecylbenzenesulfonate) was used instead of polyvinyl alcohol
Emulsion polymerization was carried out in the same manner as in Example 1, except that EVA with an ethylene content of 18.5% and a resin solid content of 55% was used.
An emulsion is obtained, and this emulsion is mixed with polyvinyl alcohol and a cationic surfactant (stearylbenzyldimethylammonium chloride).
and were added in the same amount as in Example 1 to obtain an emulsion. This emulsion
It is called EVA-2. A cement mortar test piece was obtained in the same manner as in Example 1 except that EVA-2 was used.
Each characteristic value was measured and listed in Table 1. Example 3 Using a nonionic surfactant (polyoxyethylene nonyl phenyl ether) and a cationic surfactant (stearylbenzyldimethylammonium chloride), an EVA emulsion with an ethylene content of 18% and a resin solid content of 55% was prepared. To this emulsion, polyvinyl alcohol and a cationic surfactant (stearylbenzyldimethylammonium chloride) were added to the emulsion at a ratio of 2
%, 0.5%. This emulsion is referred to as EVA-3. A cement mortar test piece was obtained in the same manner as in Example 1 except that EVA-3 was used, and each characteristic value was measured and listed in Table 1. Example 4 Emulsion polymerization was carried out in the same manner as in Example 1 except that hydroxyethyl cellulose was used instead of polyvinyl alcohol, and the ethylene content was 18% and the resin solid content was
Obtain a 55% EVA emulsion, and add hydroxyethyl cellulose and a cationic surfactant (lauryl trimethyl ammonium chloride) to this EVA emulsion at 1% of the emulsion.
It was added at a concentration of 0.5%. This emulsion is referred to as EVA-4. A cement mortar test piece was obtained in the same manner as in Example 1 except that EVA-4 was used, and each characteristic value was measured and listed in Table 1. Control example 1 Using a nonionic surfactant (polyoxyethylene noniphenyl ether) and polyvinyl alcohol, emulsion polymerization was carried out using ethylene, vinyl acetate, and a catalyst (diacetyl peroxide), and the ethylene content was 17.5% and the resin was An EVA emulsion with a solid content of 53% was obtained. This emulsion is referred to as EVA-5.
A cement mortar test piece was obtained in the same manner as in Example 1 except that EVA-5 was used, and each characteristic value was measured and listed in Table 1. Control example 2 Using a cationic surfactant (stearylbenzylmethylammonium chloride) and polyvinyl alcohol, emulsion polymerization was performed using ethylene, vinyl acetate, and a catalyst (diacetyl peroxide), and the ethylene content was 17.5% and the resin solid content was 55% EVA emulsion (3.5% each of polyvinyl alcohol and cationic surfactant to emulsion)
%, containing 0.5%). This emulsion is referred to as EVA-6. A cement mortar test piece was obtained in the same manner as in Example 1 except that EVA-6 was used, and each characteristic value was measured and listed in Table 1.

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Claims (1)

[Scope of Claims] 1 (A) a water-soluble resin; (B) a cationic surfactant selected from at least one of long-chain alkyltrimethylammonium chloride and long-chain alkylbenzylmethylammonium chloride, and (A) A cement composition comprising an ethylene-vinyl acetate copolymer emulsion and cement, which are obtained by post-adding components () and (B) to the emulsion. 2 (A) a water-soluble resin and (B) at least one of long-chain alkyltrimethylammonium chloride and long-chain alkylbenzyldimethylammonium chloride
Contains a cationic surfactant selected from seeds,
and a cement composition comprising an ethylene-vinyl acetate copolymer emulsion, cement, aggregate and/or filler, which is obtained by post-adding component (A) and component (B) to the emulsion. 3. The cement composition according to claim 1 or 2, wherein the water-soluble resin is a cellulose derivative. 4. The cement composition according to claim 1 or 2, wherein the water-soluble resin is a polyacrylic acid derivative. 5. The cement composition according to claim 1 or 2, wherein the ethylene-vinyl acetate copolymer emulsion is an ethylene-vinyl acetate copolymer emulsion having an ethylene content of 10 to 30% by weight.