JPH027904B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The polymer cement composition of the present invention has excellent flexibility and provides a non-adhesive film. The composition of the present invention is useful as a coating material for structures such as wood and concrete, a coating material for metals such as steel pipes, a mastic material, and a backing material for carpets. [Prior art] Waterproofing paints containing an aqueous resin emulsion as a main component and adding cement to this (5 to 50 parts by weight of cement per 100 parts by weight of solid resin content of the emulsion) are known (Japanese Patent Application Laid-Open No. 1989-1993). −66938, Tokko Akira
50-29731). These waterproof paints are made of polymer cement mortar (Japanese Patent Application Laid-Open No. 48-1972), which has cement as its main component and aqueous resin emulsion mixed therein at a ratio of 3 to 50% by weight (solid content) based on the sum of cement and aggregate. −
No. 44327, No. 51-1526, No. 52-81331, No. 54-
No. 66937, No. 55-10433, No. 55-104955, No. 56
−17968, No. 56-145148, No. 56-164048,
It has the advantage of providing a film with excellent elasticity and waterproof properties compared to Japanese Patent Publication No. 56-33334). The film formed from the aqueous resin emulsion containing this cement has the advantage of being non-adhesive at room temperature (Special Publication No. 50-29731). It has the advantage that it can also be used as a paint. The paint that provides a non-adhesive coating described in this Japanese Patent Publication No. 50-29731 consists of (A) component C 80% by weight or more of acrylic acrylate of _{4 to 10} and 0.5 to 10% by weight of acrylic acid or methacrylic acid. Aqueous emulsion of acrylic copolymer obtained from mixed monomers (B) Component Nonionic surfactant (C) Component Cement Component (B) is 0.1 to 100 parts by weight of the resin content of component (A) above. This is an anionic paint containing 10 parts by weight and 5 to 50 parts by weight of component (C). In this paint, the acrylic acid or methacrylic acid forming the resin of the aqueous emulsion performs a crosslinking reaction with the cement and contributes to reducing the tackiness of the film. [Problems with the prior art] The use of large amounts of unsaturated acids such as acrylic acid
This is not preferable because it reduces the flexibility of the film and also reduces the storage stability of the cement-containing composition. Furthermore, if non-adhesiveness is attempted to be achieved by increasing the amount of cement blended in the copolymer emulsion without using an unsaturated acid as a copolymer component, the flexibility of the film will deteriorate significantly, which is not desirable. do not have. [Specific measures to solve the problem] N as a copolymer aqueous dispersion added to cement.
- By using an emulsion of a copolymer of maleimide derivatives such as phenylmaleimide and other monomers, it is possible to provide a film with excellent flexibility and non-stick properties even when a large amount of cement is mixed. can. That is, the present invention provides (A) component: a minimum amount obtained by emulsion polymerization of 0.2 to 10% by weight of a maleimide derivative represented by the general formula () or () and 99.8 to 90% by weight of another copolymerizable monomer. Aqueous dispersion of a copolymer with a film-forming temperature of 0°C or lower [In the formula, X is -H, -CH ₃ , -OH, -Cl, -
OCH ₃ or -COOH; R has 1 carbon number
-4 alkyl group or cyclohexyl group. ] (B) Component: Hydraulic cement For 100 parts by weight of the solid content of the copolymer in the aqueous dispersion of (A) above, the hydraulic cement of (B) is contained in an amount of 50 to 50 parts by weight.
A polymer cement composition is provided in which the composition is blended in a proportion of 500 parts by weight. In the present invention, the minimum film forming temperature of component (A) is 0°C.
The following copolymer aqueous dispersion uses an anionic or nonionic surfactant or a protective colloid as an emulsifier, and 0.2 to 10% by weight of the maleimide derivative of () or () above in the presence of a polymerization initiator. Preferably, it is an aqueous anionic resin emulsion obtained by emulsion polymerization of 0.5 to 2% by weight and 99.8 to 90% by weight of other vinyl monomers in a conventional manner. 0.2% by weight of maleimide derivative
If it is less than that, the effect of improving the flexibility of the obtained film is too small. Even if it exceeds 10% by weight, only a hard film will be obtained. Examples of maleimide derivatives include N-phenylmaleimide, N-(methyl)phenylmaleimide, N-phenylmaleimide, and N-phenylmaleimide.
-(Hydroxy)phenylmaleimide, N-(methoxy)phenylmaleimide, N-benzoic acid maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-n.
Propylmaleimide, Nn.butylmaleimide, N-isobutylmaleimide, Nt.butylmaleimide, etc. can be used. The copolymer monomers reacted with this maleimide derivative include 2-ethylhexyl acrylate (-85°C), n-butyl acrylate (-54°C), ethyl acrylate (-22°C), isopropyl acrylate (-5 ℃), 2-ethylhexyl methacrylate (-5℃), vinylidene chloride (-18℃), n-propyl acrylate (8℃), n-propyl methacrylate (81℃), styrene (100℃), acrylonitrile ( 100℃), methyl methacrylate (105℃),
n-butyl methacrylate (20℃), vinyl acetate (30℃), ethylene (118℃), ethyl methacrylate (65℃), vinyl chloride (79℃), acrylic acid (106
°C), methacrylic acid (130 °C), acrylamide (153 °C), methacrylamide, N-methylolmethacrylamide, etc. are used one or more kinds. Note that the number in parentheses indicates the glass transition point of a homopolymer obtained from these monomers. The type and amount of these polymeric monomers are selected so that the minimum film-forming temperature of the resulting aqueous emulsion copolymer is 0° C. or lower. This minimum film-forming temperature has a strong correlation with the physical properties of the resulting film, such as flexibility, adhesion, and extensibility. The lower the minimum film forming temperature, the better the flexibility and extensibility of the film. Conversely, the higher the minimum film-forming temperature, the higher the rigidity of the film, and the more the film tends to exhibit non-adhesion. Aqueous resin emulsions with a minimum film-forming temperature of 0° C. or lower have the advantage of forming a film at room temperature (20° C.), that is, can form a film by natural drying, and are therefore easy to use at construction sites. Of course, it is also possible to perform forced heating drying using a heating means. The glass transition temperature of the copolymer is determined by conventional methods, for example from measurements of the elastic modulus when testing creep as a function of temperature, or using DTA (Differential Thermal Analysis). The aqueous resin emulsion of component A is produced with a resin concentration of 40 to 60% by weight by emulsion polymerizing these polymerizable monomers using an emulsifier or a protective colloid, and this is further diluted with water. You may also use it as The resin particle size of the emulsion is generally 0.1 to 3 microns. Examples of emulsifiers include the following. Sodium dialkyl sulfone succinate, sulfated oil sodium salt, sodium salt, sodium salt, potassium salt and ammonium alkyl sulfate of alkyl sulfonic acids, alkali metal salts of sulfonic acids, oxyalkylated C ₁₂ -C ₂₄ -aliphatic alkali metal salts of alcohols and oxyalkylated alkylphenols, as well as other oxyethylated fatty acids,
Fatty alcohols and/or fatty amides, oxyethylated alkylphenols, and also sodium salts of fatty acids such as sodium stearate and sodium oleate. Examples of protective colloid agents include polyvinyl alcohol, polyacrylic acid sodium salt, CMC, polyvinylpyrrolidone, and the like. The emulsifier or protective colloid is often used in an amount of 0.2 to 3% by weight based on the resin content. Next, the hydraulic cement of component (B) includes ordinary Portland cement called Portland cement, white cement, early strength cement, ultra early strength cement, mixed cement (blast furnace cement, silica cement, fly ash cement), etc. It will be done. The hydraulic cement of component (B) is 50 parts by weight of the solid content of the copolymer in the aqueous dispersion of (A).
It is used in a proportion of ~500 parts by weight, preferably 80-200 parts by weight. If it is less than 50 parts by weight, only the function of cement aggregate can be expected, and the mechanical strength of the film will not improve. Furthermore, the resulting film may not be sufficiently non-adhesive. On the other hand, if it exceeds 500 parts by weight, the film becomes brittle and has poor flexibility. (B) Part of the cement component is talc, mica,
Diatomaceous earth, kaolin, quartz, iron powder, fly ash, ultra white, titanium oxide, calcium carbonate, asbestos powder, white carbon, zirconia,
Aggregates such as carbon black, perlite, zinc oxide, mica, expanded polystyrene particles, perlite particles, and glass sphere particles may be used instead. When these aggregates are used, in addition to the emulsion resin of component (A), the hydraulic cement of component (B) also has a binder function, so that these aggregates are prevented from falling off from the coating. In addition to these components (A) and (B), viscosity stabilizers, antifoaming agents, solvents, plasticizers, etc. can be blended. The aqueous resin dispersion composition of the present invention can be applied to concrete, mortar, slate, iron, aluminum, fiber, wood, glass, and plastics such as vinyl chloride and polyethylene by a method such as brushing or spraying with a spray gun. It is possible to form a coating film with a thickness from the micron order to several millimeters in one cycle. Next, the present invention will be explained in detail using Examples and Comparative Examples. Parts and percentages in Examples and Comparative Examples are by weight unless otherwise specified. Example 1 2-Ethylhexyl acrylate (2EHA) 40 parts n-butyl acrylate (BA) 30 parts Styrene (St) 27.8 parts Methacrylamide (M.AAmide) 1.0 part N-phenylmaleimide 0.5 parts Acrylic acid 0.7 parts Dodecyl Sodium benzenesulfonate 1.5 parts Polyoxyethylene nonylphenol ether
A mixture of 1.5 parts potassium persulfate, 1.0 parts ion-exchanged water, and 100 parts was subjected to an emulsion polymerization reaction at 90°C for 4.5 hours.
An emulsion having a solid content concentration of 50%, a resin particle size of 0.5 microns, and a minimum film forming temperature of 0° C. or lower was obtained. To 100 parts of this emulsion, ordinary Portland cement manufactured by Ube Industries, Ltd. (specific gravity 3.1) and heavy calcium carbonate particles (specific gravity 2.7) with a particle size of 1.5 microns were added as shown in Table 1.
A paint was prepared by blending in the proportions shown below. This paint was applied to a release steel plate coated with silicone resin so that a film with a wall thickness of 2 mm was obtained, and after being left to dry naturally at 20°C for one day, the film was removed from the release steel plate. Peel off this film for 20 minutes.
It was cured for 10 days in a room at ℃. This film was evaluated for non-adhesion, tensile elongation, and tensile strength using the following methods. The results are shown in Tables 1 and 2. Evaluation method: Non-adhesiveness of the film: A sheet of paper is drawn on top of each sample, a 500g weight is placed on top of it, and when the weight is removed after 1 hour, the case where the sheet sticks to the sample is evaluated as × (adhesive). The sample was evaluated as 0 (no stickiness) if the paste did not stick to the sample. Tensile elongation, tensile strength: According to JIS A-6910. Examples 2 to 9, Comparative Examples 1 to 10 Paints were prepared and evaluated in the same manner as in Example 1, except that emulsions obtained using the monomers shown in Tables 1 to 3 were used as emulsions. The results are shown in the same table.

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[Table] Ruamide

Claims (1)

[Claims] 1 (A) Component: Obtained by emulsion polymerization of 0.2 to 10% by weight of a maleimide derivative represented by the general formula () or () and 99.8 to 90% by weight of another copolymerizable monomer. Aqueous dispersion of a copolymer with a minimum film forming temperature of 0°C or less [In the formula, X is -H, -CH ₃ , -OH, -Cl, -
OCH ₃ or -COOH; R has 1 carbon number
-4 alkyl group or cyclohexyl group. ] (B) Component: Hydraulic cement For 100 parts by weight of the solid content of the copolymer in the aqueous dispersion of (A) above, the hydraulic cement of (B) is contained in an amount of 50 to 50 parts by weight.
A polymer cement composition containing 500 parts by weight.