JP3212573B2 - Sheet molding composition such as stone-like sheet, and method for producing sheet using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to
The present invention relates to a sheet molding composition having a bark-like, earth-wall-like, or wood-grain-like surface appearance, and a method for producing a sheet using the same.

[0002]

2. Description of the Related Art Conventionally, this type of sheet contains a hydraulic inorganic cement powder, an aqueous resin emulsion, foam particles such as silas balloon, and a non-hydraulic inorganic powder such as calcium carbonate. After shaping the composition and the aqueous slurry of such a composition,
Heating to 60 ° C. for curing and drying has been proposed (JP-A-5-338399, JP-A-5-339).
No. 043). And such a conventional sheet,
It has good releasability during sheet molding and exhibits not only a surface appearance similar to the required appearance such as bark, but also freezing stability and resistance to bending when used outdoors for civil engineering applications. It has a rich and excellent effect.

[0003]

However, the prior art constructed as described above has the following disadvantages. 1. First, since the molded sheet is made of hydraulic inorganic cement as a base material, the cured and dried sheet is 5 mm thick.
In case of 〜１０10 mm, 140 ° C. for 60 minutes, 8 mm〜15
In the case of mm, it is required at 140 ° C. for 5 hours. As described above, since the heating temperature at the time of curing / drying needs to be set as extremely high as 140 ° C., not only there is a problem in terms of a heat source, a large consumption of heat source energy, or safety, but also there is a problem. As the sheet becomes thicker, the curing / drying time becomes longer, and the production efficiency is very poor. 2. Secondly, since a large amount of hydraulic mineral cement is used as a base material, a large amount of calcium hydroxide is generated in the process of hydration reaction of hydraulic mineral cement, and this flows out to the concrete surface. It easily reacts with carbon dioxide in the air to produce efflorescence. 3. Third, because a large amount of hydraulic mineral cement is used,
The cement of the unhydrated reaction tends to remain, and thus hardens and loses its elasticity under long-term water immersion.

The present invention solves the problems of the prior art described above and combines an aqueous resin emulsion together with a hydraulic cement together with a latent hydraulic inorganic powder to provide flexibility and hot water resistance with almost no efflorescence. An object of the present invention is to provide a sheet-forming composition such as a grain-like sheet which is excellent in productivity and high in production efficiency, and a method for producing a sheet using the composition.

[0005]

In other words, the invention according to claim 1 is characterized in that 100 parts by weight of a base material comprising 50 to 93 parts by weight of latent hydraulic inorganic powder and 7 to 50 parts by weight of hydraulic cement, 0-50 parts by weight of powder, 0-300 parts by weight of non-hydraulic inorganic powder, 0.5-5.
0 parts by weight, aqueous resin emulsion (resin solid content) 40
-100 parts by weight,
The gist of the present invention is a sheet molding composition such as a stone-like sheet.

The invention according to claim 2 is characterized in that 100 parts by weight of a base material comprising 50 to 93 parts by weight of latent hydraulic inorganic powder and 7 to 50 parts by weight of hydraulic cement, 0 to 50 parts by weight of pozzolan-reactive inorganic powder, Aqueous slurry of a composition containing 0 to 300 parts by weight of a hydraulic inorganic powder, 0.5 to 5.0 parts by weight of a hydration reaction retarder, and 40 to 100 parts by weight of an aqueous resin emulsion (resin solid content). Is coated or poured into a mold of a required shape and allowed to react by drying,
The gist is a method for producing a sheet such as a stone-like sheet.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate in the present invention comprises a latent hydraulic inorganic powder and a hydraulic cement.

In general, blast furnace slag can be suitably used as the above-mentioned latent hydraulic inorganic powder. Such blast furnace slag is obtained by quenching molten slag discharged from a blast furnace with water to make lime-lime aluminosilicate glassy, and its chemical components are CaO, Al2O3, M
It is composed of gO or the like, and exhibits latent hydraulicity, that is, hydraulicity in the presence of an alkaline stimulant. Esment (registered trademark) manufactured by Nippon Steel Chemical Co., Ltd. and K-cement (registered trademark) manufactured by Kobe Steel Ltd. can be used as the blast furnace slag. Latent hydraulic inorganic powder as a base material is 50 to 9 parts by weight in 100 parts by weight of the base material.
It is blended in a ratio of 3 parts by weight. And when the compounding ratio is 50 parts by weight or less, the white bleeding phenomenon strongly occurs, and
It becomes hard under long-term water immersion. If the amount exceeds 93 parts by weight, the hydraulic property is reduced and, as a result, not only the water resistance is reduced but also the film swells when immersed in warm water.

[0009] Hydraulic cement as a base material is a soil hardening cement such as Portland cement, early-strength cement, blast-furnace cement, silica cement, fly ash cement, white cement, alumina cement, Thomas ceramics cement or Beton element. And the like are used alone or in combination as needed. And the hydraulic cement as a base material is blended in a ratio of 7 to 50 parts by weight based on 100 parts by weight of the base material. At this time,
Blast furnace slag, silica, and fly ash in such hydraulic cement are each calculated as a latent hydraulic material, that is, a pozzolan-reactive component. When the compounding ratio is 7 parts by weight or less, the function of the accelerating reactant as an alkali stimulant and the effect of the cement itself are small, and as a result, the hydraulic reaction is weakened and the water resistance is reduced. Also, 50
When the amount exceeds the weight part, the efflorescence phenomenon is apt to occur, and it becomes hard after long-term immersion in water.

As the pozzolan-reactive inorganic powder of the present invention, artificial pozzolans such as fly ash, silica fume and rice hull ash, or natural pozzolans derived from shirasu, clay and volcanic ash are used in the form of fine powder. Fly ash is preferably used. In addition, the normal shirasu,
Fillers rather than such pozzolan-reactive minerals
Act as The pozzolan-reactive inorganic powder, which is mainly used as sand, reacts with a residual alkali component in the base material to form a hydrate. Such a pozzolan-reactive inorganic powder is used for the substrate 1
The amount is 0 to 50 parts by weight, preferably 30 parts by weight or less based on 00 parts by weight. When the compounding ratio exceeds 50 parts by weight, the curing reaction is delayed, so that not only the stability of the sheet becomes unstable but also This causes abnormal reaction and coloring due to impurities in fly ash.

Examples of the non-hydraulic inorganic powder include calcium carbonate, silica sand, talc, clay, ceramic particles,
In addition, various inorganic pigments and inorganic coloring pigments can be exemplified. Such a non-hydraulic inorganic powder is not necessarily an essential component, but is preferably blended as a filler. The mixing ratio is 0 to 300 parts by weight, preferably 3 parts by weight, per 100 parts by weight of the latent hydraulic inorganic powder.
0 to 150 parts by weight. If the compounding ratio is too large, the obtained sheet is hard and brittle, and particularly when immersed in water, it becomes extremely hard.

The hydration reaction retarder of the present invention suppresses and delays the hydration reaction of cement, especially when the moisture content is high in the early stage of drying under heating, so that the cracking of the sheet due to the rapid reaction is prevented. This prevents a decrease in elasticity and the like, and allows a stable hydration reaction to be performed. As such a hydration reaction retarder, sodium gluconate, sodium oxalate, or the like is used, and its blending ratio is preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of the base material. And
When the amount is less than 0.5 parts by weight, the effect of delaying the hydration reaction is negligible. Can not obtain the initial target.

As the aqueous resin emulsion, for example, 2-ethylhexyl acrylate, n.
Butyl, ethyl acrylate, isopropyl acrylate,
2-ethylhexyl methacrylate, n-propyl acrylate, n-butyl methacrylate, vinyl acetate, acrylic acid, n-propyl methacrylate, styrene, methyl methacrylate, methacrylic acid, maleic anhydride, itaconic acid, acrylamide, methacryl Emulsion of homopolymer or copolymer obtained by emulsion polymerization of one or more unsaturated monomers selected from ethyl acid, ethylene, butadiene, etc., and two types of emulsions of these polymers The above mixture is used. Also, an aqueous emulsion of a curable resin such as an aqueous epoxy emulsion can be used. Furthermore, urethane emulsions, aqueous urethane solutions, and silicone emulsions can also be used.

[0014] These aqueous resin emulsions are available from Sumikaflex (registered trademark) S-
401, S-420, Acronal (registered trademark) S-400, YJ30 manufactured by BASF Dispersion Co., Ltd.
It is commercially available under trade names such as 42D and YJ3031D.
The above-mentioned Acronal S-400, Acronal Y
J3042D is an aqueous emulsion of an acrylate-styrene copolymer resin. The Tg of the aqueous resin emulsion is preferably 5 ° C or lower, and more preferably -20 to -50 ° C. These aqueous resin emulsions are preferably used in an amount of 40 wt.
It is advisable to mix at a ratio of 100 parts by weight (resin solid content). If the compounding ratio is too large, the composition may be soft, but the surface tackiness is strong and easily stained, and the curing / drying time during molding, especially the time required for drying, becomes longer, and the productivity is reduced. Further, if the proportion is too small, sheets such as stone-like sheets become hard and brittle.

In the present invention, since the latent hydraulic inorganic powder is mainly used, an alkaline stimulant is required, and the alkaline substance of the hydraulic cement acts as the alkaline stimulant. When the compounding amount of is small, it is preferable to use an alkaline stimulant in combination, whereby a more stable hydraulic reaction can be advanced. As such an alkaline stimulant, a strong alkaline substance such as calcium hydroxide, sodium hydroxide, sodium silicate and sodium metasilicate is used. Then, the alkaline stimulant destroys the glass structure of the blast furnace slag and causes CaO, SiO2, A
It has the effect of accelerating the elution of l2O3 and MgO and increasing the concentration of each ion in the liquid phase to continuously precipitate hydrates. That is, the chain bonds of the three-dimensional network of irregular -O-Si-O-Al-O- constituting the vitreous of the blast furnace slag are cut due to the strong alkali of the alkaline stimulant, Ca, M incorporated in this network structure
Modified ions such as g and Al are easily eluted, and each eluted ion forms calcium silicate hydrate or calcium aluminate hydrate and hardens. In addition,
Such an alkaline stimulant causes the surface of the blast furnace slag to reach PH1.
It only needs to be raised to around 2 and once the reaction starts, the alkali component eluted from the blast furnace slag itself
H can be maintained. For this reason, the alkaline stimulant is added at a mixing ratio of 0 to 15 parts by weight with respect to 100 parts by weight of the blast furnace slag. If the mixing ratio exceeds 15 parts by weight, excessive alkaline content may cause efflorescence or water resistance. This is not preferable because of the possibility of causing environmental pollution and the like due to deterioration of the properties and elution of excess alkali. If the hydraulic reaction does not proceed, the freezing cycle (−20 ° C.)
Resistance to freezing in the air and thawing in 5 ° C water).

In order to form a sheet using the sheet-forming composition such as a stone-like sheet of the present invention, the composition is further kneaded sufficiently after adding water as required. Then, the mixture is made into an aqueous slurry having an appropriate water content, and then is applied to a decorative form having a predetermined unevenness or pattern such as a stone shape, or is poured and molded. At this time, the prepared aqueous slurry
May be poured at once into a decorative form and molded.
Alternatively, a part of the prepared aqueous slurry or another aqueous slurry may be previously applied to the inner surface of the decorative form to form a dry film, and then the prepared aqueous slurry may be poured and molded. In addition, as the above-mentioned decorative formwork, while using a material such as foamed polystyrene, polypropylene, polyester, urethane rubber, and silicon to form a required unevenness or a negative pattern, the inner surface of the form is easily removed. To form a release surface, use a material with a different polarity such as polyolefin, polyester, silicone, fluorine resin, enamel, urethane, or Teflon, or use a release agent such as oil, silicone oil, or a cream. It may be applied. Then, when the molding is completed, it is heated and dried at a temperature of 30 ° C. to 70 ° C. in a state of being set in the decorative mold frame to be cured. At this time, the drying temperature may be room temperature, but it is effective to heat it because it takes time.

[0017] The molded sheet may be sprayed with an appropriate powdery coloring material on the outer surface thereof for the purpose of further increasing the likeness of the stones or enhancing the strength, or may be provided with a cement-based coloring paint or clear material. -A paint or the like may be applied.

The stone-shaped sheet or the like manufactured as described above includes not only a flat structure and a curved structure such as a concrete structure, a concrete secondary product, or a steel plate, but also a cylindrical body or a sheet. Adhered to the outer surface of the rod-shaped body, it is used as a sheet with excellent durability indoors and outdoors to match the natural environment and surrounding scenery.

[0019]

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments. Examples 1 to 6 and Comparative Examples 1 to 7 The components were blended based on the blending ratios shown in Table 1 and kneaded with a mixer to adjust the aqueous slurry. Next, the aqueous slurry was poured into a required decorative mold and molded into an average of 5 mm, and then produced under the sheet manufacturing conditions shown in Table 1 to obtain a sheet.

For each of the sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 7, bendability and elasticity, efflorescence / elasticity in each case after immersion in water at 20 ° C. and 60 ° C.・
Investigate appearance, freeze cycle, and tackiness,
Table 2 shows the results of the evaluation.

As is clear from Table 2, the examples are more resistant to bending than the comparative examples, and always have proper elasticity not only at the time of formation but also when immersed in water at 20 ° C. and 60 ° C. It can be understood that they are excellent in freezing stability and non-adhesiveness without causing the efflorescence phenomenon.

Note that the above-mentioned bending property is achieved by placing a cylinder having a diameter of 20 mm on the surface of the sheet, and sealing along the cylinder.
The state when the sheet was bent by 180 degrees was visually inspected and evaluated according to the following criteria. ◎ --- No abnormality at all. ○ --- It takes some time for the bent portion of the sheet to return to the original state. Δ −−− The habit remains at the bent portion of the sheet. × --- The sheet is broken.

The above elasticity is measured by placing a sheet on a plywood (thickness: 10 mm) with its back face up and pressing it at 2 kg / cm 2, and then examining the compression deformation after releasing the pressure. The evaluation was based on criteria. ◎ ---- There is compression deformation. ○--There is some compression deformation. Δ---There is almost no compression deformation.

Further, sheet efflorescence, elasticity and appearance after immersion in water at 20 ° C. and 60 ° C. were evaluated according to the following criteria. The elasticity was evaluated according to the same criteria as described above. ○---There is no abnormality visually. X --- Abnormal whitening, swelling and warping are observed.

In the freezing cycle, after immersing in water at 5 ° C. for one day, a freezing cycle test was performed by repeating the process at -20 ° C. for 2 hours and at 5 ° C. water for 2 hours. The freezing cycle was evaluated according to the following criteria. ◎ −−− 300 cycles or more ○ −−− 200 cycles or more × −−− 100 cycles or more

[0026]

Since the present invention is constructed as described above, compared with the conventional example in which an aqueous resin emulsion is mainly combined with a hydraulic cement, the hydraulic cement and the aqueous cement are mainly composed of latent hydraulic inorganic powder. Because it is a combination of resin emulsions, it hardly causes efflorescence, is excellent in flexibility and hot water resistance, and has high production efficiency and is a grain-like sheet.
The required sheet such as a sheet can be generated.

[0027]

[Table 1]

[0028]

[Table 2]

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Claims (2)

(57) [Claims] 1. A base material comprising 50 to 93 parts by weight of a latent hydraulic inorganic powder and 7 to 50 parts by weight of hydraulic cement, 0 to 50 parts by weight of a pozzolan-reactive inorganic powder, and 0 to 50 parts by weight of a non-hydraulic inorganic powder. 300 parts by weight, hydration reaction retarder 0.5
A sheet-forming composition, such as a stone-like sheet, characterized by containing -5.0 parts by weight and 40-100 parts by weight of an aqueous resin emulsion (resin solid content). 2. 100 parts by weight of a base material comprising 50 to 93 parts by weight of latent hydraulic inorganic powder and 7 to 50 parts by weight of hydraulic cement, 0 to 50 parts by weight of pozzolan-reactive inorganic powder, 0 to non-hydraulic inorganic powder. 300 parts by weight, hydration reaction retarder 0.5
An aqueous slurry of a composition containing about 5.0 to 5.0 parts by weight and an aqueous resin emulsion (resin solid content) of 40 to 100 parts by weight is applied or poured into a mold having a required shape to cause a dry reaction. A method for producing a sheet such as a stone-like sheet.