JP2640376B2 - High strength composite material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a high-strength composite material mainly composed of a non-hydraulic inorganic material. More specifically, the present invention relates to a high-strength composite material mainly composed of a non-hydraulic inorganic material that can be used for an interior material, an exterior material, and the like, which are building materials.

2. Description of the Related Art Hydraulic inorganic materials represented by cement are widely used as structural materials and building materials. However, although the cured cement has high compressive strength, it has a drawback of low flexural strength, and attempts to improve this have been actively made. For example, it is known to use a water reducing agent to reduce the amount of added water, or to add silica fume or blast furnace slag powder to make the structure of the hardened cement dense and increase the strength. Has not been reached. The present inventors knead and mold a mixture composed of hydraulic cement, a water-soluble polymer, and water, and immediately perform a drying treatment to obtain a cured product having a flexural strength of 1000 kgf / cm ² or more. It has been found that a cured product having a flexural strength of 1000 kgf / cm ² or more can be obtained even when a mixture of a hydraulic inorganic material, a water-soluble polymer, and water is similarly treated, and a patent application has already been filed.

Problems to be Solved by the Present Invention However, the cured product obtained as described above has a problem in water resistance, and in particular, a cured product mainly composed of a non-hydraulic inorganic material is melted from the surface when contacted with water, There is a problem that the shape cannot be maintained.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention kneads and molds a mixture consisting of a non-hydraulic inorganic material, an anionic water-soluble polymer, and water, and then immerses it in an aqueous solution of a metal salt that is dissolved in water to generate a divalent or higher cation. To provide a high strength composite material which is dried. Hereinafter, the present invention will be described in detail.

First, in the present invention, the non-hydraulic inorganic material is an inorganic material that does not harden by kneading with water, and specific examples thereof include blast furnace slag powder, silica fume, fly ash, silica sand, silica stone powder, calcium carbonate, talc, Examples include bentonite, clay, zeolite, perlite, diatomaceous earth, kaolin, alumina, titania, zirconia, and the like. These may be used alone or in combination of two or more.

There is no particular limitation on the anionic water-soluble polymer that can be used. However, it is desirable that the anionic water-soluble polymer be uniformly and rapidly dissolved in the kneading system within the kneading time. For example, the following water-soluble polymers are used. That is, carboxymethylcellulose, sodium alginate, anionic polyvinyl alcohol, anionic polyvinyl acetate, poly (meth) acrylic acid, sodium poly (meth) acrylate, sodium polystyrenesulfonate, (meth) acrylic acid (or sodium thereof) (Meth) acrylic acid (or its sodium salt)
A water-soluble copolymer of a vinyl compound and an addition-polymerizable vinyl compound represented by (meth) acrylic acid ester can be used. Particularly preferred anionic water-soluble polymers are sodium polyacrylate and carboxymethylcellulose. The use amount of these water-soluble polymers is preferably 1 to 15%, more preferably 3 to 15%, based on the non-hydraulic inorganic material.
~ 10%. If the amount of the water-soluble polymer is 1% or less, the mixture cannot be kneaded, or even if kneaded, the kneaded body tends to be brittle and the moldability in the subsequent process tends to deteriorate. The effect of the present invention is not significantly changed even if it is used at 15% or more, which is economically disadvantageous.

The amount of water used depends on the type of non-hydraulic inorganic material and the type and amount of water-soluble polymer used and must be determined so that the mixture shows good kneading properties. 5 to 40%, preferably 7 to 30%
%.

In the present invention, a metal salt which is dissolved in water to generate a divalent or higher cation is used. Specific examples thereof will be described below.

Group I b element such as copper, copper group element, group II a element such as magnesium and calcium, alkaline earth metal element, group II b element such as zinc, zinc group Element, an earth element which is a group IIIa element represented by scandium, a boron group element which is a group IIIb element represented by aluminum, a titanium group element which is a group IVa element represented by zirconium, IV, represented by tin
Group b element, such as carbon group element, vanadium element group such as vanadium, vanadium group element represented by vanadium, nitrogen group element represented by group V element b represented by group V element, and VI group represented by chromium
Chromium group element which is group a element
Group VI represented by manganese, an oxygen group element that is a group VIb element
Manganese group element which is group VIIa element, iron group element represented by group VIII element represented by iron and platinum, platinum group element, and rare earth element represented by cesium, sulfate of divalent or higher metal, Among the salts such as hydrochloride, nitrate, phosphate, acetate and hydroxide, those which dissolve in water can be used. Industrially, magnesium chloride, calcium chloride, aluminum chloride, iron chloride, magnesium sulfate, aluminum sulfate, iron sulfate,
It is preferable to use copper sulfate or the like. The concentration of the metal salt aqueous solution at the time of use may be any concentration as long as it is within the range of the dissolution concentration, but it is preferable to use the concentration of 5% to 40% (weight ratio). It is preferable to select a metal salt that can prepare an aqueous solution falling within the range.

Next, a method for producing the composite material of the present invention will be described. In the present invention, a non-hydraulic inorganic material, a water-soluble polymer and water are used, and these are firstly mixed together and roughly mixed by a mixer such as a paddle type mixer or a planetary mixer. Next, kneading is performed. For kneading, a device that gives a strong shearing force to the crude mixture is used. Although there is no particular limitation on the molding machine, calender rolls, (low to high) pressure presses, (vacuum) extruder molding machines and the like are generally used. In particular, it is preferable to use a method capable of molding under reduced pressure, for example, using a vacuum extruder, since a cured product having higher bending strength and less variation in bending strength properties can be obtained. After molding, the molded body is immersed in an aqueous solution of a divalent or higher metal salt. The immersion time depends on the concentration of the metal salt aqueous solution, but is preferably about half a day to three days. If the time is too short, the water resistance becomes insufficient. The water resistance does not change significantly even when immersed for a long time.

Unlike the case where a hydraulic cement is used, the curing of the molded body does not require a curing step, and has a characteristic that a cured body can be obtained only by drying. The drying temperature is not particularly limited and is usually from 60 to 90 ° C., but may be dried at room temperature under a low humidity of 50% (relative humidity) or less. It is preferable to adopt a method of gradually drying (preliminary drying) at room temperature and then heating and drying at a high temperature (for example, 80 ° C.) for 5 to 15 hours, because the distortion of the cured product due to drying can be reduced.

The high-strength composite material of the present invention is not only excellent in bending strength and flexural modulus but also extremely excellent in water resistance.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but it is needless to say that the present invention should not be limited thereto. In the examples, parts are parts by weight.

Examples 1 to 5. Blast furnace slag powder (manufactured by Nippon Steel Corporation;
P); 100 parts and sodium polyacrylate (manufactured by Nippon Kayaku Co., Ltd .; Panakayak-B); 7 parts were placed in an omni mixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.) and mixed. Next, 16 parts of water was added to the mixture, and the mixture was mixed again. This mixture was kneaded under high shear for 5 minutes in a two-roll kneader. The dough is clay-like,
Using a vacuum extruder (Honda Iron Co., Ltd .; HDE-2 type), it was formed into a plate having a width of 10 cm and a thickness of 4 mm. This molded product was cut with a knife to prepare a large number of uncured samples having a length of 8 cm and a width of 1.5 cm, which were divided into six samples. 20% for each sample
Magnesium chloride aqueous solution (Example 1), 20% calcium chloride aqueous solution (Example 2), 20% aluminum chloride aqueous solution (Example 3), 20% copper sulfate aqueous solution (Example 4), 10% iron sulfate aqueous solution (Example) 5) Room temperature (10 ~ 20 ℃)
Immersion for 1 day in a constant temperature and humidity chamber at 30 ° C and 50% RH.
After standing for a day, a heating drying treatment was performed for 8 hours in a hot air dryer at 80 ° C., and a three-point bending test and a water resistance test were performed.

As a comparative test, leave it in a constant temperature / humidity chamber at 30 ° C and 50% RH for 1 day without immersion in the above-mentioned metal salt aqueous solution, then 80 ° C
Heat drying treatment was performed for 8 hours using a hot air dryer, and a three-point bending test and a water resistance test were performed.

(Comparative Example 1) The three-point bending test was performed using Tensilon (manufactured by Orientec Co .; UTM-2500) under the conditions of span: 6 cm, test speed: 1 mm / min. In the water resistance test, the cured product was immersed in water for one day, and the picked-up surface was rubbed with a spoon tip to determine whether or not the non-hydraulic inorganic material was dissolved. Table-Results
It is shown in FIG. The specific gravity is the specific gravity of the cured product. (Same below) Examples 6 to 8. The same treatment as in Examples 1 to 5 was performed except that carboxymethyl cellulose (manufactured by Daicel Chemical Industries, Ltd .; CMC-160); 10 parts and water; 23 parts were used as the water-soluble polymer. Was. The metal salts used were magnesium chloride, calcium chloride, and aluminum chloride, and the concentration of the aqueous solution was 20%. Further, a comparative experiment was performed according to Comparative Example 1. Table 2 shows the results.

Examples 6 to 11. Talc (manufactured by Kunimine Industries, Ltd .; Hitachi Talc HT-30)
0) 100 parts, water-soluble polymer and water of the type and amount shown in Table 3 below were mixed with an omni mixer (Chiyoda Giken Kogyo Co., Ltd.)
) And mixed. Next, the amount of water shown in Table 3 was added to the mixture, and the mixture was mixed again. This mixture was kneaded under high shear for 5 minutes in a two-roll kneader. The kneaded material is clay-like, sandwiched between two upper and lower polyethylene terephthalate films, 300 kgf / cm ²
Was pressed under pressure to obtain a plate-like molded product having a thickness of 4 mm. The same processing as in Examples 1 to 5 was performed on this molded product. For comparison, those not treated with the aqueous metal salt solution were also measured. The results are shown in Table-3.

Examples 12 to 23. Non-hydraulic inorganic materials of the type shown in Table 4 below: 100
Example 1 except for using 7 parts by weight, water amount and sodium poly-acrylate (manufactured by Nippon Kayaku Co., Ltd .; Banakayak-B);
The same processing as in No. 5 was performed. For comparison, properties were also examined for those not treated with the aqueous metal salt solution. The results are shown in Table-4.

As a result of the invention, a water-resistant high-strength composite material which is easy to knead and mold, has extremely high bending strength after drying, and is obtained from a non-hydraulic inorganic material.

Claims (1)

(57) [Claims] 1. A mixture comprising a non-hydraulic inorganic material, an anionic water-soluble polymer and water is kneaded and molded, and then immersed in an aqueous solution of a metal salt which is dissolved in water to produce a divalent or higher cation. High strength composite material that is dried.