JPH05163051A - Colored composite material - Google Patents

Abstract

PURPOSE:To provide colored cured material capable of producing by a simple method and having excellent mechanical strength. CONSTITUTION:The objective composite material having excellent mechanical strength and being vividly colored cured body is obtained by kneading a composition consisting of a blast furnace granulated slag, an alkali stimulative agent, a water soluble high polymer, an ultrafine powder substance and zinc powder of 0.1-5 pts.wt. and coloring pigment of 0.1-10 pts.wt., based on 100 pts.wt. total amount of blast furnace granulated slag and ultrafine powder substance and water and forming the kneaded product and curing the formed product under wet state.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored composite material using granulated blast furnace slag. More specifically, it relates to a colored composite material that can be used as an interior material, an exterior material, a stone material, etc. as a construction material.

[0002]

2. Description of the Related Art Cement represented by Portland cement is used in various fields, mainly in the field of construction, because it is inexpensive and can develop design strength relatively easily. However, in recent years, there has been a demand for higher strength of hardened cement products. As a method of solving this problem of strengthening, Density Actieselsk AB of Denmark is developing ultra-dense cement. However, the cured product made of this ultra-dense cement has a high compressive strength of 1500 to 2000 Kgf / cm ² , but a bending strength of 200 to 200 kgf / cm ^2.
It was about Kgf / cm ² . Regarding hardened cement having a large bending strength, ICI of the United Kingdom has developed a high strength material with a bending strength of 1800 Kgf / cm ^2, but it uses expensive alumina cement as the cement and the bending strength. Is large, but inferior in water resistance,
There was a problem that the field of use was limited.

[0003]

DISCLOSURE OF THE INVENTION As a result of investigations made by the present inventors to solve the above-mentioned problems, the bending strength is high,
Moreover, we developed a high-strength composite material with excellent water resistance and applied for a patent (Japanese Patent Application No. 2-317741). However, although this composite material has high bending strength and excellent water resistance, the cured product obtained by wet curing is a dark green-blue color, probably because of a trace amount of metal compound contained in the ground granulated blast furnace slag. Therefore, even if a pigment of another color is added, there is a problem that the color of the pigment is not utilized. For that reason,
It has been desired to develop a cured product that has high strength and is colored in various colors.

[0004]

Means for Solving the Problems The present inventors have accomplished the present invention as a result of extensive studies to solve the above problems. That is, the present invention includes (1) kneading a composition containing granulated blast furnace slag, an alkali stimulant, a water-soluble polymer, an ultrafine powder, a zinc powder and / or a zinc compound, a color pigment, and water. After molding, a colored composite material obtained by wet curing,
(2) The colored composite material according to (1) above, wherein the water-soluble polymer is poly (meth) acrylic acid salt and / or carboxymethylcellulose, (3) above, wherein the ultrafine powdery substance is silica fume. (2) The colored composite material as described above,

(4) 0.1 to 100 parts by weight of the total amount of the granulated blast furnace slag and the ultrafine powdery substance is added with 0.1 to 0.1 parts of the alkali stimulant.
5 parts by weight, 1 to 10 parts by weight of water-soluble polymer, 0.1 to 5 parts by weight of zinc powder and / or zinc compound, 0.1 to 10 parts by weight of color pigment, and 5 to 40 parts by weight of water are used. However, the amount of ultrafine powder is 1 total amount of granulated blast furnace slag and ultrafine powder.
The present invention relates to the colored composite material according to the above (1), (2) or (3), which is used in an amount of 2 to 50 parts by weight in 00 parts by weight.

The present invention will be described in detail below. The granulated blast furnace slag used preferably has a Blaine value of 2000 cm ² / g or more, and particularly preferably 3000 cm ² / g or more.

The water-soluble polymer to be used is not particularly limited, but fine particles are preferable because it is preferable that the water-soluble polymer is dissolved uniformly and rapidly in the kneading system in a short time. As the water-soluble polymer, for example, the following polymers can be used.

(1) Water-soluble polymers having a carboxyl group and / or an amide group in the molecule, or salts thereof

Α-Hydroxy-polyacrylic acid, or a salt thereof, or homopolymers or copolymers of the following monomers as raw materials, or salts thereof

(Meth) acrylic amide type monomers such as acrylic amide, N, N-dimethylacrylic amide, N-methylacrylic amide;

(Meth) acrylic acid, such as (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, lithium (meth) acrylate, and 2-hydroxyethyl (or propyl) (meth) acrylate. monomer;

Vinyl monomers such as N-vinylpyrrolidone, vinyl methyl ether, styrene sulfonic acid (or sodium salt or potassium salt thereof)

(2) Cellulose derivative Hydroxypropylmethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose

(3) Polyvinyl acetate derivative Partially hydrolyzable polyvinyl acetate, cationized polyvinyl acetate, anionized polyvinyl acetate

(4) Methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate such as propyl (meth) acrylate, styrene, ethylene,
Copolymer of propylene and the above water-soluble monomer

Of these, preferred are poly (meth) acrylic acid salts such as sodium poly (meth) acrylate and potassium poly (meth) acrylate, and carboxymethyl cellulose.

The amount of these water-soluble polymers used is preferably 1 to 10 parts by weight, and particularly preferably 2 to 7 parts by weight, based on 100 parts by weight of the total amount of granulated blast furnace slag and ultrafine powder. .. If the amount of the water-soluble polymer used is too small, it will be difficult to knead the mixture, or even if it is not difficult, the moldability in the subsequent steps tends to be poor. On the other hand, if the amount is too large, the dimensional stability of the hydrated product to water tends to deteriorate.

Specific examples of the alkali stimulants that can be used include hydroxides of alkaline metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; carbonation of alkaline metals such as sodium carbonate, potassium carbonate and lithium carbonate. salt;
Alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate and lithium bicarbonate; hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide; alkaline earth metals such as calcium oxide and magnesium oxide Oxides; and sodium pyrophosphate, lithium pyrophosphate, dipotassium phosphate, tripotassium phosphate, trisodium phosphate, sodium metasilicate, potassium metasilicate and the like.

Of these alkali stimulants, sodium hydroxide, sodium carbonate and sodium metasilicate are preferred examples.

The amount of these alkali stimulants used with respect to 100 parts by weight of the total amount of granulated blast furnace slag and ultrafine powder is:
The alkali stimulant has different alkalinity, the average particle size of the granulated blast furnace slag, and the amount of water used, but is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to
3 parts by weight.

If the amount of the alkaline stimulant used is too small,
Does kneading-molding become harder to cure due to wet curing,
Alternatively, even if it is hardened, it takes a long time for wet curing, which is industrially disadvantageous. If too much alkaline stimulant is used,
Curing may be too fast and may start during the kneading-molding process.

Next, as the ultrafine powdery substance, one having an average particle size substantially equal to that of the granulated blast furnace slag, preferably one order smaller than that, and more preferably two orders smaller than that is used. The average particle diameter of the ultrafine powder is preferably 10 μm or less, more preferably 0.01 to 5 μm, and particularly preferably 0.05 to 1 μm. The average particle size of the ultrafine powder is 1/2 to the average particle size of the granulated blast furnace slag.
It is preferably 1/1000.

The following are examples of specific ultrafine powdery substances that can be used. Silica fume, fly ash, silica sand, silica stone powder, clay, talc, kaolin, calcium carbonate, ground ceramics, slowly cooled blast furnace slag grounds, titania, zirconia, alumina, aerosil, etc.

Among these, particularly preferable examples are:
Examples include silica fume. These ultrafine powders are used in an amount such that the proportion of the granulated blast furnace slag and the ultrafine powder in 100 parts by weight is preferably 2 to 50 parts by weight, more preferably 5 to 30 parts by weight. ..

The amount of water used to obtain the colored composite material of the present invention depends on the type and amount of the water-soluble polymer, the type and amount of the alkaline stimulant, and the type and amount of the ultrafine powder substance. Differently, it must be determined so that the mixture exhibits good kneading properties, but preferably 5 to 40 parts by weight, particularly preferably 10 to 10 parts by weight based on 100 parts by weight of the total amount of the granulated blast furnace slag and the ultrafine powdery substance. 30 parts by weight.

Although the reason for the zinc powder and / or the zinc compound used in the present invention is not clear, it suppresses the generation of dark green blue that would occur when these substances are not added, and the color of the cured product after wet curing is suppressed. It has the effect of whitening and the effect of prolonging the setting time of kneading and molding. The addition amount of the zinc powder and / or the zinc compound is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the granulated blast furnace slag and the ultrafine powder substance.

If the amount of zinc powder and / or zinc compound added is too small, a deep green-blue color, which is considered to be due to the metal compound contained in the blast furnace slag described above, develops, and the required amount of the color pigment becomes very large. .. Further, even if it is used more than necessary, the action of eliminating the dark green-blue color does not change, and the setting time of the kneading-molded product becomes too long, which is disadvantageous in the manufacturing process.

Specific examples of the zinc compound include zinc hydroxide, zinc oxide, zinc sulfate, zinc nitrate, zinc chloride, zinc acetate and zinc propionate.

The color pigments to be used can be roughly classified into organic pigments and inorganic pigments. In consideration of material cost, it is preferable to use inorganic pigments, for example, iron oxide, lead white, red lead, yellow lead, silver vermilion, ultramarine. , Dark blue, cobalt oxide, titanium oxide, cobalt oxide, strontium chromate, titanium yellow, titanium black, iron black, molybdenum red, molybdenum white, lithopone, litharge, zinc chromate and the like.

The amount of these color pigments used varies greatly depending on the type of color pigment used and the type of other materials used, but with respect to the total amount of granulated blast furnace slag and ultrafine powder substance of 100 parts by weight. It is preferably 0.1 to 10 parts by weight. If the amount is too small, the coloring effect is small, and even if it is added more than necessary, the coloring effect does not change, which is economically disadvantageous.

Next, a general method for producing the colored composite material of the present invention will be described. First, granulated blast furnace slag, water-soluble polymer, ultrafine powdery substance, alkali stimulant (alkaline stimulant is preferably dissolved in water and preferably added after mixing powder components), zinc powder and / or The zinc compound and the coloring pigment are put into an oscillating mixer or a planetary mixer such as an omnimixer (manufactured by Chiyoda Giken Kogyo Co., Ltd.) and powder-mixed. Next, a predetermined amount of water or an alkaline solution in which an alkaline stimulant is dissolved is added to this mixture, and further mixed (coarse kneading). Next, the kneading is started, but it is preferable to use an apparatus capable of giving a strong shearing force to the coarse kneaded product. For example, a roll kneader, a Banbury mixer, a wet Banbury mixer, a mixing roll, a bag mill, a pressure kneader, a screw extruder, a kneader ruder, or the like is used, and kneading is performed until the kneaded product has a clay-like shape.

The molding machine is also not particularly limited, and calender rolls, (low to high) pressure presses, (vacuum) extruders and the like are generally used. Especially a method that can be molded under reduced pressure,
For example, when a vacuum extruder or a vacuum press is adopted, a colored composite material having greater bending strength and less variation in bending strength physical properties can be obtained, which is preferable.

Further, by adding a color pigment to the kneaded product at the final stage of the kneading process, stopping the kneading to such an extent that the color pigment is not uniformly distributed in the kneaded product, and carrying out molding-wet curing to give a shade of color. A cured product can also be manufactured.

After molding, the process is transferred to wet curing. It is necessary to carry out the wet curing at least in the kneading-high humid atmosphere in which the water in the molded body does not evaporate. 80% relative humidity
Or more, preferably 90% or more, more preferably 100%
Wet curing is performed in the atmosphere. In such a high-humidity atmosphere, the evaporation of water in the molded product may be performed by placing the molded product in a container or bag that is impermeable to moisture, or by sandwiching the molded product between plastic plates, plastic films, and metal plates. Wet curing may be performed by a method capable of preventing the above. It is also possible to carry out curing in water by immersing the molded body in the initial stage of wet curing in water. In the present invention, the higher the wet curing temperature, the faster the kneading to the curing of the molded body, but generally a temperature of room temperature to 100 ° C is used. Further, autoclave treatment may be performed at a temperature of 100 ° C. or higher using steam.

The time for wet curing depends on the type and amount of the alkaline stimulant used and the conditions for hydration hardening, but it is about half a day to 7 days.

Since the cured product after wet curing contains water, it is preferable to dry such a cured product before use. The drying temperature is usually freely selected from the temperature of room temperature to 100 ° C.

Further, in obtaining the colored composite material of the present invention, fibrous substances such as pulp, vinylon, polypropylene fiber, polyethylene fiber, carbon fiber and aramid fiber may be added, or silica sand may be used as a fine aggregate. , Silica stone powder, wollastonite, sepiolite, minestone,
Zeolite, bentonite, slowly cooled blast furnace slag, etc. can be added.

The colored composite material of the present invention is a cured product which is easy to manufacture, has excellent mechanical strength such as compressive strength and bending strength, and is colored beautifully.

[0039]

The present invention will be described in more detail based on the following examples, but it goes without saying that the present invention is not limited thereto. In addition, in the examples, "part" means "part by weight".

Example 1 90 parts of granulated blast furnace slag (manufactured by Nippon Steel Chemical Co., Ltd .; Essment (brain value; 4000 cm ² / g)), 10 parts of silica fume (manufactured by Nippon Heavy Chemical Industry Co., Ltd.), as a water-soluble polymer , Sodium polyacrylate (Nippon Kayaku Co., Ltd.)
Made; Panakayak B) 3 parts, zinc oxide (reagent) 0.5 parts,
Also, 1.0 part of a red inorganic pigment (manufactured by Bayer; Bayferrox Red 120NM) was placed in an omni mixer and powder-mixed for 4 minutes. An aqueous alkaline stimulant solution consisting of 1.0 part of sodium hydroxide and 14 parts of water was added to this powder mixture, and the mixture was further stirred and mixed (coarse kneading) for 3 minutes. Next, this crude kneaded material was kneaded with a two-roll kneader under high shearing force for 5 minutes to obtain a kneaded material. The kneaded material was clay-like, and when the setting time at 20 ° C was measured by the needle penetration method,
It was 12 hours.

This kneaded product was extruded into a plate having a width of 10 cm and a thickness of 4 mm under a reduced pressure of 740 mmHg with a vacuum extrusion machine (HDE-2 manufactured by Honda Iron Works Co., Ltd.). The molded product obtained in this way is heated at 90 ° C. and 100% R
The sample was placed in the H humidifying chamber and subjected to wet curing for 48 hours. The obtained colored composite material of the present invention had a beautiful red color. This cured product (colored composite material) was cut into a size of 8 cm in length and 1.5 cm in width with a band-shaped diamond cutter,
The bending property was measured and the color was measured. For bending properties, Tensilon (manufactured by Orientec Co., Ltd.) was used, and the pressurizing speed;
At 1 mm / min, and colorimetric spectrophotometer (manufactured by Macbeth;
A color eye 2020 plus) was used to measure the L ^* value, a ^* value, and b ^* value, which are color systems of CIE (International Commission on Illumination). The results are shown below.

Bending strength Kgf / cm ² 620 Flexural modulus Kgf / cm ² , × 10 ⁵ 3.10 L ^* value 50.32 a ^* value 22.77 b ^* value 16.47

Example 2 5 parts of potassium polyacrylate as water-soluble polymer, 18 parts of water, 2.5 parts of sodium metasilicate as alkali stimulant, 0.7 parts of zinc powder, yellow inorganic pigment (Bayer) Manufactured by Biferox Yellow 420) except that 3 parts are used,
The same operation as in Example 1 was carried out to obtain the colored composite material of the present invention. The colored composite material had a beautiful yellow color. The results of the bending property measurement and color measurement performed in the same manner as in Example 1 are shown below.

The potassium polyacrylate used in this example was synthesized by a conventional method using a 35% potassium acrylate aqueous solution with potassium persulfate as a polymerization initiator. The intrinsic viscosity [η] of the obtained potassium polyacrylate was 0.6.
It was 9, which was almost equivalent to 0.72 of sodium polyacrylate used in Example 1. The setting time of the kneaded material in this system was 7 hours.

Bending strength Kgf / cm ² 640 Bending elastic modulus Kgf / cm ² , × 10 ⁵ 3.25 L ^* value 60.87 a ^* value 7.00 b ^* value 33.28

Example 3 As a water-soluble polymer, 7 parts of carboxymethyl cellulose (Daiichi Kogyo Seiyaku Co., Ltd .; serogen BSH-12), 20 parts of water, 1.2 parts of sodium hydroxide as an alkali stimulant, The same procedure as in Example 1 was performed except that 1.5 parts of zinc oxide (reagent) and 5 parts of a green inorganic pigment (Bayer Co .; chromium oxide GN) were used to obtain a colored composite material of the present invention. .. The color of this colored composite material was a beautiful green color.
The setting time of the kneaded material in this system was 15 hours. The results of the bending property measurement and color measurement performed in the same manner as in Example 1 are shown below.

Bending strength Kgf / cm ² 680 Bending elastic modulus Kgf / cm ² , × 10 ⁵ 3.17 L ^* value 58.62 a ^* value-12.54 b ^* value 12.17

Example 4 85 parts of granulated blast furnace slag (Nippon Steel Chemical Co., Ltd .; Essment (Blaine value; 4000 cm ² / g)), 15 parts of silica fume (manufactured by Nippon Heavy Chemical Industry Co., Ltd.), and poly as a water-soluble polymer 3 parts sodium acrylate ([η] = 0.11 in 1N NaOH), 1.0 part zinc oxide (reagent),
And 3 parts of a white inorganic pigment (manufactured by Bayer; titanium oxide A) were placed in an omni mixer and powder-mixed for 3 minutes. To this powder mixture, an aqueous alkaline stimulant solution consisting of 2.0 parts of sodium hydroxide and 30 parts of water was added, and the mixture was further mixed by stirring.
After a minute, the mixture became fluid. The kneaded product was poured into a mold having a width of 1.5 cm, a thickness of 1 cm, and a length of 8 cm, and was wet-cured for 1 week in saturated humidity at 20 ° C. The obtained cured product was a white color, which was similar to that of a white cement cured product. The results of the bending property measurement and color measurement performed in the same manner as in Example 1 are shown below.

Flexural strength Kgf / cm ² 270 Flexural modulus Kgf / cm ² , × 10 ⁵ 2.21 L ^* value 71.58 a ^* value 0.11 b ^* value 1.99

Comparative Example 1 The same operation as in Example 1 was carried out except that zinc oxide was not used. As shown below, the bending properties of the cured product are almost the same as those of the cured product of Example 1, but the setting time of the kneaded product is as short as 1 hour, and the color of the cured product after wet curing and drying is as follows.
It was a cloudy color with a mixture of red and green-blue.

Bending strength Kgf / cm ² 655 Bending elastic modulus Kgf / cm ² , × 10 ⁵ 3.12 L ^* value 29.42 a ^* value 7.42 b ^* value 7.24

[0052]

Industrial Applicability The colored composite material of the present invention is a composite material using inexpensive granulated blast furnace slag, which has high strength and is sharply colored in various colors inside.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C04B 24:26 E 2102-4G 24:38) B 2102-4G (72) Inventor Masayuki Kiyomoto Saitama 1476-5, Sachigawa, Omiya-shi, Japan

Claims (4)

[Claims] 1. After kneading and molding a composition containing granulated blast furnace slag, an alkali stimulant, a water-soluble polymer, an ultrafine powder, a zinc powder and / or a zinc compound, a color pigment, and water, Colored composite material obtained by wet curing. 2. The colored composite material according to claim 1, wherein the water-soluble polymer is poly (meth) acrylic acid salt and / or carboxymethyl cellulose. 3. The colored composite material according to claim 1, wherein the ultrafine powder substance is silica fume. 4. The total amount of granulated blast furnace slag and ultrafine powdery substance 1
0.1 to 5 parts by weight of an alkali stimulant, 1 to 10 parts by weight of a water-soluble polymer, 0.1 to 5 parts by weight of zinc powder and / or a zinc compound, and 0 to 0 parts by weight of a coloring pigment. 1 ~
10 parts by weight, 5 to 40 parts by weight of water are used, and the amount of ultrafine powder is 2 to 50 parts by weight in the total amount of 100 parts by weight of granulated blast furnace slag and ultrafine powder. The colored composite material according to claim 1, 2 or 3, which is used.