JPH11240744A - Highly strong glass polymer cement hardened material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly strong hardened material by kneading and solidifying a hydraulic cement, natural silicate mineral particles, a large amount of glass particles and a water-soluble synthetic resin emulsion. SOLUTION: (A) The hydraulic cement comprises ordinary Portland cement, etc., but is preferably white cement. (B) The natural silica mineral includes iron tourmaline and garnet which are ground into particles having sizes of 5-250 μm. (C) The glass particles have particle sizes of 150 μm to 10 mm. (D) The water-soluble synthetic resin emulsion includes an emulsion prepared by diluting an acrylic-styrene copolymer resin or vinyl acetate-ethylene-vinyl chloride copolymer with water in a concentration of 20-40 wt.%. The components A, B, C and D are compounded in amounts of 10-90 pts.wt., 10-90 pts.wt., 20-180 pts.wt. and 20-50 pts.wt., respectively. The components are homogeneously dispersed, deaired, aged, molded and subsequently hardened to give the hardened material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of recycling waste glass waste material which has lost its value for use in foods and beverages and as a building material, as a method of recycling a large amount of waste glass waste into a mixture of hydraulic cement and natural silicate minerals. The present invention relates to a high-strength glass polymer cement solidified material which is mixed, kneaded and solidified with a water-soluble synthetic resin emulsion, and a method for producing the same.

[0002]

2. Description of the Related Art At present, recycling of waste is an important issue in Japan from the viewpoints of environmental protection and effective use of resources, and there are many proposals. As a method of treating and recycling glass waste materials, there is a method of mixing glass waste materials with a hardening agent, asphalt, cement, or the like, and using the mixture for road pavement or reclaiming a digging site as a solidified product (Japanese Unexamined Patent Application Publication No. No. 154458) or processed into glass beads and used as a concrete containing glass beads as an enhancer for a light reflection plate of a structure (Japanese Patent Laid-Open No. 6-1994).
No. 340458) has been proposed.

However, in the case of road pavement such as asphalt, the maximum mixing ratio of glass waste material is about 10 to 15%, and glass beads are mixed in ready-mixed concrete mixed with cement, sand and gravel as disclosed in JP-A-6-340458. In the use of a structure with light for light reflection, 3 to 3
Only about 5% can be mixed. Although effective in terms of reusing glass waste material, the effect is small in terms of utilizing a large amount of glass waste material because the glass content is small.

[0004]

Originally, when glass is mixed with hydraulic cement, the silicate component, which is a glass composition, causes a chemical reaction (alkali-aggregate reaction) with the alkali component of the hydraulic cement, resulting in a cement crystal. It causes a change in the composition inside, causing deterioration phenomena such as expansion, peeling and cracking. Therefore, a large amount of glass waste cannot be used as aggregate of the solidified concrete. An object of the present invention is to provide a high-strength glass-polymer cement solidified material that is used as a building and civil engineering material such as bricks, tiles, and large-sized inner and outer wall materials utilizing a large amount of glass waste material, and a method for producing the same.

[0005]

According to the present invention, a large amount of waste glass waste is processed into fine glass particles together with fine particles of a natural silicate mineral and used as a reinforcing aggregate for hydraulic cement. It has been found that kneading with a resin emulsion results in a glass polymer cement solidified material with high strength.

That is, tourmaline [NaFe ₃ Al ₆ B ₃ Si ₆ (OH) ₃₀ ] and garnet [Fe ₃ Al ₂ (SiO ₄ ) ₃ ], which are natural silicate minerals, are each bipolar crystals. Because of this, the crushed fine particles have independent bipolar crystals, which when contacted with water, electrolyze water due to the electrical properties of natural silicate minerals, and convert water to hydrogen ions (H ⁺ ). Decomposes into hydroxyl ions (OH ⁻ ). At that time, the positive ions (H ⁺ ) are released as hydrogen gas (H ₂ ) because of their high ion mobility, but the hydroxyl ions (OH ⁻ ) combine with surrounding water molecules (H ₂ O) [ H ₂ O
+ OH ⁻ = (H ₃ O ₂ ) ⁻ ], hydroxyl ion (H
_It has been found that the substance changes into a surfactant called ₃ O ₂ ) ^- , which causes a surfactant effect.

In the present invention, utilizing this property, fine particles and fine glass particles of a natural silicate mineral are added as a reinforcing aggregate to a hydraulic cement and mixed with a water-soluble synthetic resin emulsion. The surfactant effect of the emulsion is promoted. As a result, the affinity between the hydraulic cement and the resin component is increased, and a copolymer in which the crystalline structure of the cement and the water-soluble synthetic resin are densely entangled with each other is exhibited, exhibiting high bending characteristics and compression characteristics. Furthermore, the water-soluble resin forms a resin film between the cement crystalline composition and the glass due to the surfactant effect of water. As a result, it was found that the glass was not in direct contact with the cement crystalline composition, the reaction between the cement and the glass was prevented, and a glass polymer cement material having extremely high strength was obtained even when a large amount of glass was added. Until now, the strength of the solidified body was reduced when glass swarf was mixed into hydraulic cement.However, fine particles of natural silicate mineral added as aggregate of hydraulic cement and water-soluble synthetic resin emulsion It has been found that there is a possibility of utilizing a large amount of glass waste material utilizing the synergistic effect, and the present invention has been completed.

The hydraulic cement of the present invention may be any of ordinary bolt land cement, early-strength cement, white cement, and alumina cement. In the present invention, white cement was used. A rotary beating mill was used to grind the natural silicate mineral and the glass swarf. The particle size of the natural silicate mineral may be about 5 μm to 250 μm, and the particle size of the glass may be about 150 μm to 10 mm. As the coloring pigment, either an inorganic pigment or an organic coloring agent may be used. Examples of water-soluble synthetic resin emulsions include vinyl acetate emulsions, vinyl acetate / acrylic copolymer resin emulsions, vinyl acetate / ethylene copolymer resin emulsions, acrylic copolymer resin emulsions, acrylic / styrene copolymer resin emulsions, and vinyl acetate / ethylene copolymers.・ In addition to using one or more vinyl chloride copolymer resins, add appropriate amount of water to these powders together with hydraulic cement, fine powder (or granules) of natural silicate mineral, and fine glass powder (or granules) Thus, a cement-water-soluble synthetic resin emulsion can be prepared. In the present invention, as a water-soluble synthetic resin emulsion, acrylic
A styrene copolymer resin and a vinyl acetate / ethylene / vinyl chloride copolymer resin diluted with water and adjusted to a concentration of 20 to 40% by weight were used. The solidified high-strength glass-polymer cement of the present invention comprises 10 to 90 parts by weight of fine powder (or grains) of natural silicate mineral, and 20 pieces of fine glass powder (or grains).
To 180 parts by weight and 10 to 90 parts by weight of white cement, and 20 to 50 parts by weight of a water-soluble synthetic resin emulsion. Water-soluble synthetic resin emulsion is 20 ~
The content may be within the range of 50 parts by weight, but preferably 35 to 45 parts by weight in consideration of the viscosity of kneading.

In the production method of the present invention, a fine powder (or granules) of a natural silicate mineral, a hydraulic cement and a fine glass powder (or granules) are preliminarily mixed and prepared to have the above-mentioned composition and weight composition. After uniformly dispersing the mixed composition and the water-soluble synthetic resin emulsion by a kneader, the mixture is filled in a plate-shaped form, deaerated, cured, and solidified to obtain a high-strength glass polymer cement solidified material.

[0010] Specific examples of the molding method of the present invention include known molding methods such as extrusion, rolling, and mold filling, and combinations of the above-mentioned known methods. A known method such as a known curing solidification method such as curing under pressure and steam curing may be used.

A specific example of the cutting process of the present invention may be a known method using a diamond cutter, a water jet or the like. In the cutting process, the plate-like solidified body may be cut in the length direction or the width direction or both directions, or the block-shaped or lump-shaped solidified body may be cut in the thickness direction.

That is, the solidified high-strength glass polymer cement of the present invention may be obtained by molding into a required shape in advance, or may be obtained by cutting to obtain a required shape. Moreover, the obtained solidified body is large and small tiles, bricks, plates, and the like that are used as construction and civil engineering materials.

In addition to the above-mentioned features of the method for producing a high-strength glass-polymer cement solidified material of the present invention, energy consumption is suppressed because it is not baked at a high temperature, and production at normal temperature and pressure is possible. It is characterized by an earth-friendly manufacturing method from the viewpoint that environmental protection is first. Hereinafter, the present invention will be described in more detail with reference to examples.

[0014]

Embodiment 1 Hydraulic cement (white cement) 70
Parts by weight, 70 parts by weight of fine particles of tourmaline, which is a natural silicate mineral as a reinforcing aggregate, and 60 parts by weight of fine glass particles, are mixed with an acrylic / styrene copolymer resin (solid content) as a water-soluble synthetic resin emulsion. (30% by weight), kneaded with 43 parts by weight to form a cream, and molded into a mold. After solidification and demolding, a strength test was conducted 14 days after curing. As a comparative example, a strength test result when natural sand is used instead of the natural silicate mineral is also described. JIS for compressive strength test
R-5201, bending strength test conformed to JIS A-1408. As a result, a compression strength of 696 Kgf / cm ² and a bending strength of 161 Kgf / cm ² were obtained. The value of the comparative test using natural sand in place of the natural silicate mineral showed a compressive strength of 2
The bending strength was 42 Kgf / cm ² and the bending strength was 87 Kgf / cm ² .

[0015]

Embodiment 2 Hydraulic cement (white cement) 70
Parts by weight, 70 parts by weight of fine particles of garnet, which is a natural silicate mineral, and 60 parts by weight of fine glass particles as a reinforcing aggregate were mixed with an acrylic / styrene copolymer resin (solid content: 30) as a water-soluble synthetic resin emulsion. (% By weight) and kneaded with 43 parts by weight to form a cream, and then molded into a mold. After solidification and demolding, 14 days after curing, the same strength test as in Example 1 was performed. The resulting high-strength glass polymer cement board had a compressive strength of 735 Kgf / cm ² and a flexural strength of 189 Kgf / cm ² .

[0016]

Embodiment 3 Hydraulic cement (white cement) 70
By weight, 70 parts by weight of fine particles of tourmaline, which is a natural silicate mineral as a reinforcing aggregate, and 60 parts by weight of fine glass particles, are copolymerized with a water-soluble synthetic resin emulsion of vinyl acetate / ethylene / vinyl chloride. Resin (solid content 30% by weight) 4
After kneading with 3 parts by weight to form a cream, the mixture was molded into a mold. After solidification and demolding, 14 days after curing, the same strength test as in Example 1 was performed. The resulting high-strength glass-polymer cement board has a compressive strength of 672 Kgf / cm.
^{2. The} bending strength was 145 kgf / cm ² .

[0017]

Embodiment 4 Hydraulic cement (white cement) 70
Parts by weight, 70 parts by weight of fine particles of garnet, a natural silicate mineral as a reinforcing aggregate, and 60 parts by weight of fine glass particles, are vinyl acetate / ethylene / vinyl chloride copolymer resins which are water-soluble synthetic resin emulsions. (Solid content 30% by weight) 4
After kneading with 3 parts by weight to form a cream, the mixture was molded into a mold. After solidification and demolding, 14 days after curing, the same strength test as in Example 1 was performed. The resulting high-strength glass-polymer cement board has a compressive strength of 715 Kgf / cm.
^{2. The} bending strength was 153 Kgf / cm ² .

[0018]

Embodiment 5 Hydraulic cement (white cement) 70
Parts by weight, 70 parts by weight of fine particles of iron tourmaline, a natural silicate mineral as a reinforcing aggregate, and 60 parts by weight of fine glass particles, are copolymerized with a vinyl acetate / ethylene / vinyl chloride copolymer as a water-soluble synthetic resin emulsion. Resin (solid content 30% by weight) 2
0 parts by weight and an acrylic / styrene copolymer resin (solid content 30
(% By weight) and kneaded with 23 parts by weight to form a cream, and then molded into a mold. After solidification and demolding, 14 days after curing, the same strength test as in Example 1 was performed. The compressive strength of the resulting high strength glass polymer cement board is 701K
gf / cm ² and bending strength 153 Kgf / cm ² .

[0019]

Embodiment 6 Hydraulic cement (white cement) 70
Parts by weight, 70 parts by weight of fine particles of garnet, a natural silicate mineral as a reinforcing aggregate, and 60 parts by weight of fine glass particles, are vinyl acetate / ethylene / vinyl chloride copolymer resins which are water-soluble synthetic resin emulsions. (Solid content 30% by weight) 2
0 parts by weight and an acrylic / styrene copolymer resin (solid content 30
(% By weight) and kneaded with 23 parts by weight to form a cream, and then molded into a mold. After solidification and demolding, 14 days after curing, the same strength test as in Example 1 was performed. The compressive strength of the resulting high strength glass polymer cement board is 748K
gf / cm ² and bending strength 198 Kgf / cm ² .

[0020]

Example 7 20 parts by weight of a vinyl acetate / ethylene / vinyl chloride copolymer resin (solid content 30% by weight) and 23 parts by weight of an acrylic / styrene copolymer resin (solid content 30% by weight), which are water-soluble synthetic resin emulsions. Table 1 shows the results of the compressive strength and flexural strength of the high-strength glass-polymer cement board obtained by using the fine particles of garnet, which is a natural silicate mineral, depending on the mixing amount of the glass particles. .

[0021]

[Table 1]

[0022]

1) High-strength glass that can be used as an architectural or civil engineering material by using a natural silicate mineral and a large amount of glass particles for hydraulic cement and kneading and solidifying with a water-soluble synthetic resin emulsion. A polymer cement solidified material was obtained. 2) The high-strength glass-polymer cement solidified material is a manufacturing method suitable for global environmental protection without being hardened using a firing furnace that generates carbon dioxide gas, NOX, SOX, and the like. 3) As a way to recycle large amounts of glass particles, a large amount of glass waste can be used.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C04B 28/02 14:22 14:04)

Claims (7)

[Claims] 1. A high-strength glass polymer cement solidified by kneading and solidifying a hydraulic cement, fine particles of a natural silicate mineral, a large amount of fine glass particles and a water-soluble synthetic resin emulsion. Wood. 2. The high-strength glass-polymer cement solidified material according to claim 1, further comprising a coloring pigment. 3. A first step of kneading a mixture of hydraulic cement, fine particles of a natural silicate mineral and a large amount of fine glass particles, and a water-soluble synthetic resin emulsion, a second step of molding, and a curing and solidifying step. A method for producing a high-strength glass polymer cement solidified material, comprising a third step of: 4. The method for producing a solidified high-strength glass polymer cement according to claim 3, wherein a color pigment is added to the mixture in the first step. 5. The method according to claim 3, wherein the second step is performed by one or a combination of extrusion, mold packing, and rolling. 6. The method according to claim 3, wherein the third step is performed by room temperature solidification or steam curing. 7. A first step of kneading a mixture of hydraulic cement, fine particles of natural silicate minerals and a large amount of fine glass particles, and a water-soluble synthetic resin emulsion, a second step of molding, and a curing step. A method for producing a high-strength glass polymer cement solidified material, comprising a third step of solidifying and a fourth step of cutting.