JP2980292B2 - High strength composite material composition and method for producing cured product 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 a high-strength composite material using a latent hydraulic material and its use.
More specifically, the present invention relates to a high-strength composite material composition that can be used as a construction material in the same manner as a conventional cement composition, and a cured product produced using the same.

[0002]

2. Description of the Related Art Latent hydraulic substances are substances which do not harden simply by being mixed with water, but which hydrate and harden when a certain stimulant is added thereto. Slag, etc. are known. These latent hydraulic substances have good durability, such as chemical resistance and seawater resistance, and have an inhibitory effect on the alkali-aggregate reaction, so they are mainly added to ordinary Portland cement to compensate for those disadvantages of cement. in use.

[0003] Among them, granulated blast furnace slag is a substance that is produced as a by-product in a large amount during the production of pig iron, and its amount reaches several tens of million tons per year, and its effective utilization is being studied in various ways. As a method of using the potential hydraulic property of granulated blast furnace slag, there is a method of adding several percent to several tens of percent to cement (ordinary Portland cement) and using it as "blast furnace cement". However, this is also a method in which granulated blast furnace slag is used as an admixture as an admixture material, and a material mainly composed of granulated blast furnace slag itself has hardly been developed. The reason is,
It is known that when water and an alkali stimulant or a sulfate stimulant are added to granulated blast furnace slag, latent hydraulic properties are exhibited and curing (hydration reaction) progresses gradually. This is because the body has a disadvantage that it is very brittle and cannot withstand use.

[0004] Accordingly, we have obtained a composition comprising granulated blast furnace slag, a water-soluble polymer, an alkaline substance and water, and a kneaded, molded, wet-cured cured product having a high mechanical strength. We have already found a patent application.

[0005]

However, in order to obtain a cured product having high mechanical strength, granulated blast furnace slag,
When kneading a composition consisting of a water-soluble polymer, an alkaline substance, and water, a kneader capable of applying a strong shearing force is required, or a long kneading time is required. There were problems such as requiring a machine.

[0006]

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 provides: (1) a high-strength composite material composition obtained by kneading, drying and pulverizing a mixture comprising a latent hydraulic substance, a water-soluble polymer, and water; -COOH group or -CO
The high-strength composite material composition according to the above item (1), which is a polymer having an O ^- group. (3) The polymer having a -COOH group or a -COO ^- group in the molecule is poly (meta). ) A high strength composite material composition according to the above item (2), which is an acrylate salt. (4) Water and an alkali stimulant are added to the high strength composite material composition according to the above item (1). And a method for producing a cured product characterized by kneading and molding. Hereinafter, the present invention will be described in detail.

First, in the present invention, the latent hydraulic substance is
Granulated blast furnace slag, converter slag, etc. These latent hydraulic substances may be used alone or in combination of two or more. Also, fly ash, silica fume and the like can be used as the admixture.

The water-soluble polymer to be used is not particularly limited, but is preferably used in the form of fine particles since it is preferable to uniformly dissolve or permeate the kneading system in a short time. Specific examples thereof include the following. Cellulose derivatives such as hydroxypropylmethylcellulose and hydroxyethylcellulose. Homopolymers or copolymers made from polyethylene oxide, α-hydroxy-sodium polyacrylate, and the following monomers.

(Meth) acrylamide monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide and (meth) acryloylmorpholine. (Meth) acrylate monomers such as (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, and ammonium (meth) acrylate. Vinyl monomers such as 2-hydroxyethyl (or propyl) (meth) acrylate, N-vinyl pyrrolidone, vinyl methyl ether, styrene sulfonic acid (or their sodium salts).

Also, a water-soluble polymer obtained by copolymerizing with the above-mentioned monomer can be used. Examples of monomers that can be copolymerized are described below. (Meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
These polymers may be used alone or in combination of two or more. Of these polymers, preferred ones are
A polymer having a COOH group and a -COO ^- group is preferable, and a poly (meth) acrylate is more preferable.

The amount of the water-soluble polymer used is usually 0.1 to 10%, preferably 1 to 7% by weight based on the latent hydraulic substance. The amount of these polymers used is 0.1
% Or less, the mixture cannot be kneaded, or even if kneaded, the moldability in subsequent steps tends to be poor. The effect of the present invention is not changed even if 10% or more is used, which is economically disadvantageous. The amount of water when kneading the latent hydraulic substance and the water-soluble polymer is desirably a small amount for the convenience of the subsequent drying step, but kneading can be easily performed and the kneaded material is efficiently dried. Therefore, it is determined so that the step of reducing the particle size becomes easy. Usually 8 to latent hydraulic substances
35% (by weight) water is used.

Next, a general method for producing the high-strength composite material composition of the present invention will be described. In the present invention, a latent hydraulic substance and a water-soluble polymer are mixed with an oscillating mixer such as an omni mixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.), a kneader-ruder mixer, a planetary mixer, a Warner kneader, or the like. Into a powder mixer and mixed in powder form. Next, a predetermined amount of water is added to the mixture, and the mixture is further mixed (coarse kneading). Next, the process proceeds to kneading. The machine used for kneading is not particularly limited. However, in order to speed up the process, it is preferable to use a device capable of giving a strong shearing force to the roughly kneaded material. For example, a roll kneader, a Banbury mixer, a wet-type Banbury mixer, a mixing roll, a knette machine, a bag mill, a screw extruder, a kneader ruder, and the like are used.
Kneading is carried out until it becomes clay-like.

In order to dry the kneaded product, it is desirable to process it into a molded product having high drying efficiency. That is, it is desirable to use a pelletizer, a meat chopper, or the like to make a thin string or granule. The dryer used for drying the kneaded material is not particularly limited as long as it can sufficiently remove the water used for kneading, but for speeding up the process, a ventilation dryer, a drum dryer, Using a rotary dryer, etc.
Drying is performed at a temperature of 100 ° C. or more, more preferably 130 ° C. or more. Further, there is no particular limitation on a machine for pulverizing the composite material composition obtained by drying, and a bandam mill, a ball mill, a Yariya pulverizer, a rotoplex pulverizer and the like can be used. Further, a spray dryer or the like which simultaneously performs drying and pulverization can also be used. The particle size after pulverization is preferably adjusted to 500 μm or less, preferably 200 μm or less.

Conventionally, in order to knead a composition consisting of blast furnace slag, a water-soluble polymer, an alkaline substance and water, it has been necessary to use a roll kneader, a pressure kneader, a Banbury mixer or the like, which exerts a strong shearing force. However, the high-strength composite material composition of the present invention does not require a machine that exerts a strong shearing force, and includes a concrete mixer, an omni mixer, and the like.
It can be kneaded in a mortar or the like. In addition, even when a machine with a strong shearing force is used, the kneading time is very short. As a result, the conventional cement / concrete kneading machine can be used sufficiently.

Next, a method for producing a cured product using the high-strength composite material composition of the present invention will be described. After adding the alkali stimulant and water to the high-strength composite material composition of the present invention and kneading with a concrete mixer, an omni mixer or the like as required, or kneading with a mortar or the like, molding, curing, and drying are performed by ordinary methods, and the curing of the present invention Get the body. Specific examples of the alkali stimulant to be added in this case include caustic soda, caustic potash, alkali hydroxides such as lithium hydroxide, soda ash, alkali metal carbonates such as potassium carbonate, and alkalis such as sodium hydrogen carbonate. Metal bicarbonate, calcium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide, Portland cement, potassium pyrophosphate, sodium metasilicate, potassium metasilicate, etc., among which are preferred. Is an alkali hydroxide represented by caustic soda and caustic potash. The amount of addition is 0.1 to 5.0.
% By weight, preferably. It is 0.5 to 3.0% by weight. When the use amount of the alkali stimulant is 0.1% or less, the composite material composition does not cure, or even if it cures, it takes a long time to cure. On the other hand, if the amount of the alkali stimulant exceeds 5%, the curing is too fast, and there is a possibility that the operation in the curing step may be hindered. The amount of water to be used is generally 8 to 60% with respect to the composite material composition of the present invention, but the strength decreases when the amount of water used is large, and the strength increases when the amount of water used is small. There is a tendency to be.

In curing the high-strength composite material composition of the present invention, a bone agent usually used in the field of civil engineering and construction can be added. As the aggregate, for example, river sand, sea sand, mountain sand, crushed sand, slag sand, river gravel, lightweight aggregate, and the like can be used. Further, fibers or the like can be added for the purpose of improving the toughness of the cured product. Examples of fibers that can be used include, for example, glass fiber, carbon fiber, vinylon fiber, aramid fiber, polypropylene fiber, steel fiber, alumina fiber,
Cellulose fibers and the like can be mentioned. Various materials having other functions can also be added.

[0017]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts are parts by weight.

Example 1 Granulated blast furnace slag 100 having a Blaine value of 4000 cm ² / g
, A mixture of 3 parts of sodium polyacrylate (Panakayak-B manufactured by Nippon Kayaku Co., Ltd.) and 20 parts of water was kneaded with a roll kneader under high shear for 5 minutes. Cut the kneaded material into flakes with a meat chopper,
It was dried in a stream of 0 ° C. for 1 hour. Then, this was finely pulverized with a Yariya pulverizer, classified by a test screen sieve (nominal size of sieve: 150 μm), and the one that passed through the sieve was collected to obtain a composite material composition of the present invention.

Next, a solution prepared by dissolving 1 part of sodium hydroxide in 25 parts of water is added to 100 parts of the powdery composite material composition, and the mixture is kneaded in a Warner kneader to form a paste. The time until the kneading machine motor was loaded was observed. As Comparative Example 1, 3 parts of sodium polyacrylate (Nippon Kayaku Co., Ltd .: Panakayak-B) and 1 part of sodium hydroxide 1 were added to 100 parts of granulated blast furnace slag having the same Blaine value of 4000 cm ² / g as in Example 1.
Was dissolved in 25 parts of water and kneaded in a Warner kneader in the same manner as in Example 1. The time required for the kneaded material to become a paste was measured, and the state of the load applied to the motor of the kneader was measured. Was observed. Table 1 shows the results.

The analytical values of the granulated blast furnace slag used in this example were as follows. SiO ₂ 34.1%, Al ₂ O ₃ 14.2%, Fe
₂ O ₃ 0.6% CaO 42.2%, MgO 6.4%

[0021]

As is clear from the table, the latent hydraulic substance,
By previously mixing, kneading, drying, and pulverizing a composition comprising a water-soluble polymer and water, kneading can be performed in a much shorter time than when this treatment is not performed, and the load on the kneading machine is extremely low. Less.

Example 2 A composite material 100 of the present invention obtained in the same manner as in Example 1
And a mixture obtained by dissolving 1 part of sodium hydroxide in 18 parts of water was kneaded with a spiral mixer for 3 minutes, and the state of the obtained kneaded material was observed. (Table 2) As Comparative Example 2, the same brane value of Example 1 was set at 4000 cm.
^To 100 parts of granulated blast furnace slag of ² / g, 3 parts of sodium polyacrylate (Nippon Kayaku Co., Ltd .: Panakayak-B) and 1 part of sodium hydroxide dissolved in 18 parts of water were added.
Kneading was performed for 3 minutes with a spiral mixer in the same manner as in Example 2, and the state of the obtained kneaded material was observed. Table 2 shows the results.

The kneaded material obtained above is 4 mm thick by a vacuum extrusion molding machine (HDE-2 type, manufactured by Honda Iron Works Co., Ltd.).
Was subjected to vacuum extrusion. Table 2 shows the results. The obtained molded product was cured in saturated steam at 90 ° C. for 24 hours to obtain a cured product of the present invention. From this cured product, a test specimen for measuring bending properties having a width of 15 mm and a length of 75 mm was prepared, and the bending properties were measured. (Table 2) The bending properties were measured using Tensilon (UTM-2500, manufactured by Orientec Co., Ltd.) under the conditions of a span interval of 60 mm and a bending speed of 1 mm / min.

[0025]

As is clear from the table, the latent hydraulic substance,
By previously mixing, kneading, drying and pulverizing a composition comprising a water-soluble polymer and water, the kneading time can be extremely shortened, and the obtained cured product has very high strength. Was.

Example 3 Mixing, molding and curing were carried out in the same manner as in Example 2 except that 50 parts of flattery sand and 20 parts of water were used for 100 parts of the composite material composition obtained in the same manner as in Example 1. And a cured product of the present invention was obtained. The bending properties were measured in the same manner as in Example 2. Table 3 shows the results.

[0028]

By previously mixing, kneading, drying and pulverizing a composition comprising a latent hydraulic substance, a water-soluble polymer, and water, the kneading time can be shortened even when aggregate is added, The obtained cured product had very high strength.

Example 4 Granulated blast furnace slag 100 having a Brain value of 3800 cm ² / g
A mixture comprising 5 parts of carboxymethylcellulose (Daiichi Kogyo Seiyaku, Cellogen BSH-12) and 5 parts of water was treated in the same manner as in Example 1 to obtain a composite material composition of the present invention. An aqueous solution in which 1.5 parts of sodium hydroxide was dissolved in 25 parts of water was added to 100 parts of the composite material composition, and Example 2 was added.
The mixture was kneaded in the same manner as described above, and was subjected to vacuum extrusion and curing to obtain a cured product of the present invention. The bending properties of this cured product were as follows. Flexural strength (kgf / cm ² ) 380 Flexural modulus (× 10 ⁵ kgf / cm ² ) 2.12

[0031]

According to the present invention, a latent hydraulic substance and a water-soluble polymer are mixed,
By kneading, drying and pulverizing, a composite material composition having excellent moldability can be obtained which can be kneaded with a simple kneading machine after adding water and an alkali stimulant and can be performed in a short time. Was done. The composite composition provided a cured product exhibiting high mechanical strength.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-123842 (JP, A) JP-A-2-307850 (JP, A) JP-A-59-30746 (JP, A) JP-A-63-123842 282149 (JP, A) JP-A-3-290348 (JP, A) JP-A-3-237050 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C04B 28/08 B28C 7 / 00 C04B 24/26 C04B 24/38

Claims (4)

(57) [Claims] 1. A high-strength composite material obtained by kneading, drying, and pulverizing a mixture comprising a latent hydraulic substance, a water-soluble polymer, and water. 2. A or -COOH group water-soluble polymer in the molecule -COO ^- high strength composite material composition according to claim 1, characterized in that a polymer having a group. 3. The high-strength composite material according to claim 2, wherein the polymer having a —COOH group or a —COO ⁻ group in the molecule is a poly (meth) acrylate. 4. A process for producing a cured product, comprising adding water and an alkali stimulant to the high-strength composite material composition according to claim 1, kneading and molding.