JPH062327B2 - Method for producing plastic concrete molded product having uneven pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The invention of the present application is to improve the designability by selecting the optimum conditions in the curing process of a cement-containing W / O type emulsion molding and applying an uneven pattern to improve the design. The present invention relates to a method for producing a plastic concrete molded product having an uneven pattern suitable for.

[Prior art]

Cement-containing W / prepared from cement, water, and vinyl monomer solution in which surfactant and polymerization catalyst are dissolved
O type emulsion has very high viscosity and excellent moldability,
A molded product can be easily obtained by a casting method, an extrusion molding method, or the like. In order to improve the design of these molded products, an attempt was made to form an uneven pattern on the surface, but the generally known method did not achieve satisfactory results. For example, according to the casting method, it is possible to manufacture a molded article having an uneven pattern by using a mold having an uneven pattern. However, since it is impossible to remove the mold until curing of the molded product is almost completed, it is necessary to prepare a mold frame with an uneven pattern corresponding to the production amount, which is extremely uneconomical from an industrial viewpoint. Become.
On the other hand, according to the extrusion molding method, it is conceivable that the uncured cement-containing W / O type emulsion molded product immediately after extrusion molding is pressed with a mold material having an uneven pattern to shape it. Since the hardened cement-containing W / O type emulsion has strong adhesiveness, it is difficult to form an uneven pattern by adhering to the mold material.

[Means for solving problems]

By solving the above-mentioned problems, a plastic concrete molded article having an uneven pattern can be industrially and efficiently used.
As a result of examining the method for producing advantageously, cement,
A cement-containing W / O emulsion molded product prepared from water and a vinyl monomer solution in which a surfactant and a polymerization catalyst are dissolved, is used in the curing process of vinyl monomer polymerization and cement hydration reaction. At least one surface is brought into contact with air to press the mold material on which the uneven pattern is applied to the surface layer having plasticity formed by delaying the polymerization rate of the vinyl monomer to form the uneven pattern, and then the surface By further advancing the polymerization of the vinyl monomer of the layer and the hydration reaction of cement to complete the curing, the cement-containing W / O type emulsion is continuously adhered to the mold material at a relatively low press pressure. It has been found that the uneven pattern can be formed on the. As a result, it became possible to industrially advantageously and efficiently manufacture a plastic concrete molded product having an uneven pattern.

That is, the feature of the present invention is that the curing process of the cement-containing W / O type emulsion prepared from the cement, water, and the vinyl monomer solution in which the surfactant and the polymerization catalyst are dissolved is caused by the polymerization reaction of the vinyl monomer and the cement. It consists of a hydration reaction. In this case, paying attention to the fact that the preceding polymerization reaction of the vinyl monomer is delayed by contact with air, and the uneven pattern of the cement-containing W / O type emulsion molded product is given. The surface to be shaped is brought into contact with air to delay the progress of the polymerization reaction and has plasticity suitable for shaping an uneven pattern, and the time when the non-adhesive surface layer is formed is selected. The point is to form an uneven pattern by pressing a pattern-shaped mold material. At this point, the polymerization reaction of the vinyl monomer inside the molded product, which is not in contact with air, has progressed considerably and forms a hard base material layer, so it is destroyed by the pressure that forms an uneven pattern on the surface layer. There is no such thing.

The hardness of the non-adhesive and plastic surface layer formed by contacting the molded product with air is preferably about 5 to 30 on the Shore A hardness scale. Particularly preferably, it is 10 to 20. If it is less than 5, it sticks to the mold material or the formed uneven surface is easily peeled off, and therefore it is not suitable for forming a fine uneven pattern. On the other hand, when it exceeds 30, the plasticity is lowered, and thus a high pressing pressure is required to form the uneven pattern.

The Shore A hardness of the cured base material layer inside the molded product is preferably 40 or more. If it is less than 40, there is a risk of damaging the non-plastic, minute cell structure made of a vinyl polymer formed by the progress of the polymerization reaction of the vinyl monomer, by the pressing pressure.

As described above, it is desirable to avoid pressurizing the cell structure that has lost plasticity formed by the progress of the polymerization reaction of the vinyl monomer, and the depth of the uneven pattern to be shaped can be increased by contacting with air. It is preferable that the thickness is almost equal to the thickness of the formed plastic surface layer.

The mold material used for forming the uneven pattern on the molded product is not particularly limited, but a plate-shaped article on which the uneven pattern is applied,
Alternatively, a roll or the like can be considered. According to the method of the present invention, since it is possible to shape with a relatively low press pressure,
As the material of the mold material, wood material, plastic material, or the like can be used.

In the present invention, a cement-containing W / O type emulsion is produced and molded by mixing and stirring cement, water, and a vinyl monomer solution in which a surfactant and a polymerization catalyst are dissolved. ,
Although not particularly limited, examples include Portland cement, blast furnace cement, fly ash cement, silica cement, magnesia cement, and alumina cement.

As the surfactant used for producing the cement-containing W / O type emulsion, W / O which is generally used
There is no particular limitation as long as it is a surfactant for producing an O-type emulsion. For example, sorbitan sesquioleate, glycerol monostearate, sorbitan monooleate, diethylene glycol monostearate, sorbitan monostearate, polyglycerol monooleate. , A dibasic acid anhydride adduct of polyalkylene glycol, and a neutralized product thereof. These may be used alone or in combination of two or more.

The vinyl monomer used for producing the cement-containing W / O type emulsion is not particularly limited as long as it is a water-insoluble liquid monomer at room temperature, and examples thereof include styrene, α-methylstyrene, acrylate ester, Methacrylic acid ester, acrylonitrile, divinylbenzene,
Examples thereof include acrylic acid or dimethacrylic acid ester of alkylene glycol and acrylic acid or methacrylic acid ester of polyhydric alcohol. It is generally preferable to use a divinyl compound such as ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate, or a trivinyl compound.

The vinyl monomer polymerization catalyst used in the present invention may be a known radical former or redox catalyst.

The cement-containing W / O type emulsion is prepared by mixing and stirring the above-mentioned cement, water, and a vinyl monomer solution in which a surfactant and a polymerization catalyst are dissolved. Organic or inorganic fibers as a material, or lightweight aggregate as a filler may be mixed.

The molding method of the cement-containing W / O type emulsion is not particularly limited, but a casting method, an extrusion molding method and the like are suitable.

The cement-containing W / O emulsion molded product is cured by allowing it to undergo a polymerization reaction of vinyl monomers and a hydration reaction of cement when left at room temperature, but is saturated in order to accelerate the reaction and accelerate curing. It can be heated in steam.
If necessary, early-strength cement or a quick-setting agent may be used.

Obtained by the method described above, the plastic concrete molded article on which the uneven pattern is applied can be lightened by drying and volatilizing water,
Depending on the application, it can be used as a tough material with high specific gravity.

[Action effect]

The greatest feature of the present invention is that W / O containing cement
By utilizing the polymerization characteristics of the vinyl monomer of the mold emulsion, it is possible to form a fine uneven pattern clearly and efficiently on a molded product at low pressure. In the case of a mere cement molded product, even if you choose a curing condition that can shape an uneven pattern at low pressure, since it has plasticity throughout, the cement paste does not spread to every corner of the uneven pattern applied to the mold material, It is difficult to shape a fine uneven pattern clearly. On the contrary, if the press pressure is increased, the shape of the molded product itself will be lost. According to the method of the present invention, since the uneven surface pattern is formed in such a state that the surface layer having plasticity is sandwiched between the cured base material and the mold material, even if the press pressure is relatively low, The cement-containing W / O emulsion spreads everywhere, and fine uneven patterns can be clearly shaped.

The low press pressure for shaping the uneven pattern allows the use of mold materials such as plastic that are easy to mold, so a wide range of uneven patterns can be selected, and plastic concrete molding with extremely high designability Things,
Easy to manufacture.

As described above, the plastic concrete molded product obtained by the method of the present invention with the surface having an uneven pattern does not lose the original properties such as excellent lightness, flexibility, processability or tough physical properties. Since it is possible to give excellent designability, the compatibility with building materials and the like has become higher.

The present invention will be specifically described with reference to the examples.

Example 1 71.3 parts by weight of styrene monomer, 3.8 parts by weight of trimethylolpropane trimethacrylate, 2.5 parts by weight of sorbitan monooleate, and t-butyl were added to a continuous kneader having both a kneading function and an extrusion molding function. 18.6 parts by weight of a vinyl monomer solution in which 1 part by weight of peroxybenzoate is dissolved, 18 parts by hour of Portland cement
6.2 parts by weight of water, 372.0 parts by weight of water per hour, and 6 parts by weight of acrylic fiber (length 6 mm) were continuously supplied to obtain a plate-shaped molded product of a cement-containing W / O emulsion. When this was received on a plywood mold and left at 23 ° C. for 48 hours, the Shore A hardness of the surface was 10 and the Shore A hardness of the internally cured base material was 45. At this time, the mold material wound with a flexible polyester sheet having a concavo-convex pattern applied to a metal roll was rotated while being pressed against the surface of the molded product, and the concavo-convex pattern applied to the polyester sheet was obtained. It was clearly shaped on the surface of the molded product. When this molded product was cured and cured at room temperature for 5 days and then dried, a plastic concrete molded product having a light and flexible and excellent workability and having an uneven pattern was obtained.

Example 2 Obtained by mixing 60 parts by weight of a styrene monomer, 20 parts by weight of ethylene glycol dimethacrylate, 20 parts by weight of a maleic anhydride adduct of polypropylene glycol having an average molecular weight of 2000, and 1 part by weight of t-butylperoxyisobutylate. 100 parts by weight of vinyl monomer solution,
Portland cement 500 parts by weight, water 700 parts by weight,
Perlite 100 parts by weight, glass fiber (length 6 mm) 50
Cement-containing W / O emulsion prepared by mixing and stirring parts by weight using a kneader is poured into a mold, and after the surface is finished with a doctor knife, the surface is smoothed, and the surface is open for 50 hours at room temperature. When left to stand, the Shore A hardness of the surface was 15, and the Shore A hardness of the internally cured base material was 60. At this point, when the mold material with the polypropylene sheet with the uneven pattern applied to the metal plate was pressed against the molded product, the uneven pattern applied to the polypropylene sheet was clearly shaped on the surface of the molded product. It was When this molded product was cured in a curing room at a relative temperature of 100% and a greenhouse temperature of 60 ° C. for 40 hours and then dried, a light-weight and flexible plastic concrete molded product having an uneven pattern excellent in workability was obtained.

Example 3 Vinyl monomer solution 100 in which 63 parts by weight of methyl methacrylate, 7 parts by weight of trimethylolpropane trimethacrylate, 30 parts by weight of polyglycerol monooleate, and 1 part by weight of t-butylperoxybenzoate were dissolved.
600 parts by weight of blast furnace cement, 300 parts by weight of water, and 10 parts by weight of vinylon fiber (length 6 mm) are mixed and stirred in a kneader to prepare a cement-containing W / O type emulsion as a mold. After pouring and smoothing the surface with a doctor knife, the surface was opened and allowed to stand at room temperature for 46 hours. The Shore A hardness of the surface was 20, and the Shore A hardness of the internal base material was 80. At this point, a metal roll was wrapped around a polyester sheet with an uneven pattern and pressed against the surface of the molded product and rotated, and the uneven pattern applied to the polyester sheet was clearly visible on the surface of the molded product. Was shaped into. The molded product was further cured and cured at room temperature for 5 days and then dried to obtain a plastic concrete molded product having a high specific gravity but a tough uneven pattern.

Comparative Example 1 The W / O type emulsion molded product obtained in Example 1 was
Immediately after the molding, an attempt was made to form an uneven pattern by the same method as in Example 1, but the unevenness could not be formed by sticking to the rotor.

Claims (3)

[Claims] 1. A process for curing a vinyl monomer of a cement-containing W / O type emulsion molding prepared from a cement, water, and a vinyl monomer solution in which a surfactant and a polymerization catalyst are dissolved, and a hardening process by hydration reaction of the cement. At
At least one surface of the molded product was brought into contact with air, and the surface layer having plasticity formed by delaying the polymerization rate of the vinyl monomer was pressed with the mold material on which the uneven pattern was applied to shape the uneven pattern. Then, a method for producing a plastic concrete molded product having an uneven pattern, characterized by further promoting the polymerization of vinyl monomer in the surface layer and the hydration reaction of cement to complete the curing. 2. The Shore A hardness of a plastic surface layer formed by bringing the surface of a molded product into contact with air has a hardness of 5 to 30, and the Shore A hardness of the cured product therein.
The method for producing a plastic concrete molded product having an uneven pattern according to claim 1, which has a hardness of 40 or more. 3. The depth of the concavo-convex pattern to be shaped and the thickness of the surface layer having plasticity formed by contacting with air are substantially equal to each other.
A method for producing a plastic concrete molded article having an uneven pattern according to the item.