JPH10724A - Manufacture of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a double-layered laminate excellent in adhesion strength by a method wherein at least one surface of a hardened body of a slurry containing SiO2 -Al2 O3 based powder, alkali metal silicate and water is roughened so as to supply the slurry on the roughened surface and then harden it. SOLUTION: Inorganic powder A is obtained by supplying 100 pts.wt. of SiO2 -Al2 O3 based powder, 20 pts.wt. of mica, 30 pts.wt. of talc, 57.5 pts.wt. of wollastonite, 0.5 pts.wt. of vinylon into the lancaster mixer for drying for 5min. A mixture, which is prepared by adding 75 pts.wt. of alkali metal silicate, 10 pts.wt. of hydrogen peroxide water and 1 pts.wt. of zinc stearate to 100 pts.wt of the inorganic powder A and mixing them, is cast in a form of 320×320×20mm by the thickness of 10mm. The obtained slurry is heated up for 30min at 50 deg.C and then polished with blast abrasives. Onto the obtained heardened body, the slurry free from the hydrogen peroxide water and the zinc stearate is cast and hardened at 85 deg.C for 3hr. Thus, a double-layered laminate having excellent adhesion strength is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate.

[0002]

_2. Description of the Related Art A laminate comprising a cured product of an inorganic composition mainly composed of an SiO ₂ --Al ₂ O ₃ powder and an aqueous solution of an alkali metal silicate is already known (JP-A-7-30).
No. 4124). According to this method, SiO ₂ —Al
It is a laminate of a layer obtained by curing a slurry composed of a ₂ O ₃ -based powder and an aqueous solution of an alkali metal silicate, and a layer formed by adding a foaming agent to the slurry and foam-curing the slurry. The laminate having such a structure not only significantly reduces the mechanical strength but also reduces the weight of the laminate, and the main component layer includes ash of an electric dust collector and industrial waste such as combustion bauxite. We are trying to use it.

However, when a foaming agent is added to one of the layers, layer separation occurs due to a difference in specific gravity. In particular, when a sandwich structure in which a foam is disposed in the center is to be obtained, the foam and the dense body in the upper layer are mixed, and a desired structure cannot be obtained. When one layer is cured or semi-cured first, a skin layer is formed on the surface, and the adhesion strength is reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a method of manufacturing a laminate having excellent adhesion strength and capable of easily producing a multilayer laminate. I do.

[0005]

According to the present invention, there is provided a method for producing a laminate, wherein at least one of a cured product obtained by curing a slurry comprising an SiO ₂ —Al ₂ O ₃ powder, an alkali metal silicate and water. Is formed on the surface, and the slurry is supplied onto the surface to cure the slurry. The SiO ₂ —Al ₂ O ₃ -based powder used in the present invention is not particularly limited as long as it is an alkali metal silicate aqueous solution described below and can be dissolved. For example, the weight ratio is SiO ₂ / Al ₂ O. _Three
= 1/9 to 9/1 is preferred. More preferably, 2/8
８8/2.

The above-mentioned SiO ₂ —Al ₂ O ₃ powder preferably has a total content of SiO ₂ and Al ₂ O ₃ of 50% by weight or more. If it is less than 50% by weight, the reactivity with the aqueous alkali metal silicate solution is reduced. More preferably, it is 55% by weight or more.

[0007] Specific examples of the above-mentioned SiO ₂ -Al ₂ O ₃ powder are not particularly limited.
(2) Inorganic powder containing at least 80% by weight of fly ash having a particle size of 10 μm or less and fired at 400 to 1000 ° C., (3) Inorganic powder obtained by melting fly ash and clay and spraying it into a gas; (4) inorganic powder obtained by applying mechanical energy of 0.1 to 30 kWh / kg to clay; (5) ( The inorganic powder obtained by further heating the inorganic powder of 4) at 100 to 750 ° C, (6) metakaolin, and (7) metakaolin in 0.1%.
Inorganic powder obtained by applying a mechanical energy of 1 to 30 kWh / kg, (8) ash of an electric dust collector for producing corundum or mullite, (9) crushed calcined bauxite,
And the like. These can be used alone or in combination of two or more.

The inorganic powder of the above (1) has a particle size of 10 μm.
m or less fly ash. 1 above
The content of fly ash of 0 μm or less is preferably 80% by weight or more. When the content is less than 80% by weight, the reactivity with the aqueous alkali metal silicate solution is reduced, so that poor curing is caused and the strength of the obtained cured product is reduced.

The fly ash is JIS A 62
No. 01, are fine ash particles collected by a dust collector from a pulverized coal combustion boiler, SiO ₂ 40% or more, moisture 1% or less, specific gravity 1.95 or more, specific surface area 270
It passes at least 75% through a standard sieve of at least 00 cm ₂ / g and 44 μm.

The inorganic powder of the above (2) has a particle size of 10 μm.
m and 80% by weight or more of fly ash, and baked. Since the fly ash is generally black, when it needs to be colored, it is used after decoloring by firing. The firing temperature is 400 to 100.
0 ° C. is preferred. If the temperature is lower than 400 ° C., decoloring by firing cannot be performed, and if the temperature is higher than 1000 ° C., the reactivity with an alkali metal silicate aqueous solution decreases. The firing is, for example,
It can be carried out by using an electric furnace, a burner, an electron beam or the like.

The inorganic powder of (3) is obtained by melting fly ash and clay and spraying it in a gas.

The clay is not particularly limited as long as it contains ₅ to 85% by weight of SiO ₂ and 90 to 10% by weight of Al ₂ O _3. Examples of the clay include kaolinite, dickite, nacrite, halloysite and the like. Kaolin minerals; mica clay minerals such as muscovite, illite, fengite, chlorite, celadonite, paragonite, and bulmarite;
Smectites such as montmorillonite, beidellite, nontronite, sabonite, sauconite, etc .; chlorite; pyrophyllite; talc;

The above inorganic powder (4) is obtained by applying mechanical energy to clay. The clay is not particularly limited, and examples thereof include the same clays as those exemplified in the inorganic powder of the above (3). In order to make mechanical energy work effectively, Those having a thickness of 0.01 to 500 μm are preferred. More preferably, the thickness is 0.1 to 100 μm.

The mechanical energy is not particularly limited, and includes, for example, compressive force, shear force, impact force and the like. These may act alone or in combination of two or more.

The inorganic powder of (5) is obtained by further heating the inorganic powder of (4). The above heating improves the mechanical strength. The heating temperature is 100
~ 750 ° C is preferred. If the temperature is lower than 100 ° C., no improvement in mechanical strength of the obtained cured product is observed. More preferably, it is 200 to 600 ° C.

The heating time is preferably 1 minute to 5 hours. When the time is less than 1 minute, the mechanical strength of the obtained cured product is not improved much, and when it exceeds 5 hours, the energy cost increases.

The metakaolin in the above (6) is not particularly restricted but includes, for example, commercially available ones. The inorganic powder of (7) is obtained by applying mechanical energy to the metakaolin. The above-mentioned metakaolin preferably has an average particle size of 0.01 to 500 μm in order to effectively apply mechanical energy. More preferably, the thickness is 0.1 to 100 μm. The mechanical energy is the same as in (4) above.

The ash of the electric precipitator at the time of the production of corundum or mullite (8) is mainly composed of silicate glass, aluminum iron silicate glass, or the like. The pulverized calcined bauxite of the above (9) is obtained by heating the pulverized bauxite at 400 to 1000 ° C.

As the alkali metal silicate, SiO ₂ / M ₂ O (M represents an alkali metal) =
Those having a value of 0.01 to 8 are preferred. If it is less than 0.01, the content of the alkali metal with respect to SiO _{2 serving as} a binder component in the cured product is too large, and the strength of the obtained cured product is reduced. Become
Workability decreases and storage stability decreases. More preferably, it is 0.1 to 2.5. The alkali metal is not particularly limited, and includes, for example, sodium, potassium, lithium and the like. These can be used alone or in combination of two or more.

The concentration of the aqueous alkali metal silicate solution is as follows:
It is preferably from 10 to 70% by weight. If the amount is less than 10% by weight, the strength of the obtained cured product is reduced. If the amount is more than 70% by weight, the viscosity increases, and the workability during mixing and molding is reduced. More preferably, it is 10 to 60% by weight.

The amount of the aqueous alkali metal silicate solution is preferably 10 to 1000 parts by weight based on 100 parts by weight of the SiO ₂ —Al ₂ O ₃ powder. If it is less than 10 parts by weight, mixing is difficult, and if it exceeds 1300 parts by weight,
Cracks and the like occur during molding. More preferably, 10
750 parts by weight.

[0022]

The above-mentioned lightweight aggregate is not particularly restricted but includes, for example, perlite, glass balloons, silica balloons,
Inorganic foams such as fly ash balloons and shirasu foams; organic foams such as phenolic resins, urethane resins, polyethylene, and polystyrene;

The compounding amount of the above lightweight aggregate is SiO ₂ -Al
_It is preferably 150 parts by weight or less based on 100 parts by weight of the ₂ O ₃ -based powder. When the amount exceeds 150 parts by weight, the strength and surface smoothness of the obtained cured product are reduced, and the workability is reduced.

The pigment is not particularly limited, and examples thereof include metal oxide pigments such as iron oxide, titanium oxide, and cobalt oxide; and carbon black. The amount of the pigment _is preferably 50 parts by weight or less with respect to SiO 2 -Al ₂ O ₃ -based powder 100 parts by weight. If the amount exceeds 50 parts by weight, the hiding power of the obtained cured product surface is not improved, and it is uneconomical.

In the present invention, a foaming agent may be added to any layer of the laminate. As the foaming agent, Mg,
Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, A
metal powders such as 1, Ga, Sn, Si, and ferrosilicon; and peroxide powders such as hydrogen peroxide, sodium peroxide, potassium peroxide, and sodium perborate. Of these, Al and hydrogen peroxide are preferred from the viewpoints of cost, safety, availability, and ease of mixing.

The above-mentioned foaming agent has a particle size of 1 to 200 when solid.
μm is preferred. If it is less than 1 μm, the dispersibility is reduced and foaming is rapid, and if it is more than 200 μm, the reactivity is reduced. The amount of the foaming agent is
Preferably more than 5 parts by weight to SiO ₂ -Al ₂ O ₃ -based powder 100 parts by weight. If the amount exceeds 5 parts by weight, the strength of the obtained cured product is significantly reduced, and handling of the cured product becomes impossible.

In the present invention, a foaming aid may be further added, if necessary. The foaming aid is not particularly limited, and examples thereof include porous powders such as silica gel, zeolite, activated carbon, and alumina gel; and metal soaps such as metal stearate and metal palmitate. The amount of the foaming aid _is preferably 10 parts by weight or less with respect to SiO 2 -Al ₂ O ₃ -based powder 100 parts by weight. If the amount exceeds 10 parts by weight, foam breakage or the like is generated, which adversely affects foaming.

In the present invention, a foaming agent may be further added as required. The foaming agent is not particularly limited, for example, higher alcohol sulfate, alkyl ether sulfate, aromatic derivative sulfonate,
Examples include imidazoline derivatives, fatty acid amides, animal protein-based derivatives, and the like. The amount of the foaming agent is SiO ₂ -A
It is preferably 10 parts by weight or less based on 100 parts by weight of l ₂ O ₃ powder. If it exceeds 10 parts by weight, poor curing is likely to occur.

In the present invention, the above-mentioned SiO ₂ -Al ₂
O ₃ -based powder, the aqueous alkali metal silicate solution, and the inorganic filler optionally blended, the reinforcing fiber,
The above-mentioned lightweight aggregate, the above-mentioned foaming agent, the above-mentioned foaming assistant, the above-mentioned foaming agent and the like are mixed to form an inorganic composition.

In the present invention, as a method of mixing each foaming agent, foaming aid and foaming agent, the last compounding in the case described in the present invention 1 is used, or a slurry using a raw material other than the foaming agent is used. Preferably, the slurry is mixed with an aqueous solution that has generated bubbles by mixing the foaming agent and water. In this case, the concentration of the aqueous solution that has generated bubbles by mixing the foaming agent and water is
0.1-5% is preferred. If the amount is less than 0.1%, the stability of the air bubbles is poor, and the bubbles are broken. If the amount exceeds 5%, poor curing occurs. The last mixing is preferred in terms of workability and stability of bubbles.

In the present invention, the method of mixing the respective raw materials is not particularly limited. For example, a method using a mixer such as a paddle rotary mixer, an oscillating mixer, a screw mixer and the like can be adopted. In this case, after the powder raw material and the solid raw material are dry-mixed in advance, the alkali metal silicate aqueous solution may be added and mixed, or all the raw materials may be simultaneously supplied and mixed. After mixing the alkali metal silicate aqueous solution and some of the solid raw materials, other raw materials may be sequentially mixed. In the present invention, a lightweight aggregate may be added as needed. The lightweight aggregate used is not particularly limited, and examples thereof include inorganic foams such as pearlite, glass balloon, silica balloon, fly ash balloon, and shirasu foam; organic foams such as phenolic resin, urethane resin, polyethylene, and polystyrene. And the like.

The amount of the above lightweight aggregate is SiO ₂ -Al
_It is preferably 150 parts by weight or less based on 100 parts by weight of the ₂ O ₃ -based powder. When the amount exceeds 150 parts by weight, the strength and surface smoothness of the obtained cured product are reduced, and the workability is reduced.

In the present invention, if necessary, an inorganic filler, a reinforcing fiber, a pigment, a foaming agent, a foaming aid, a foaming agent and the like can be blended.

As the inorganic filler, if the alkali metal silicate aqueous solution has a high activity, the alkali metal silicate aqueous solution rapidly gels, and mixing and molding become difficult. Those having low activity with respect to the salt aqueous solution are used. Examples of such a material include, but are not particularly limited to, silica sand; rock powder; volcanic ash such as shirasu and anti-firestone; wollastonite; calcium carbonate; diatomite; mica; mica;

The compounding amount of the above-mentioned inorganic filler is SiO _2-
Preferably 900 parts by weight or less relative al ₂ O ₃ system powder 100 parts by weight. When the amount exceeds 900 parts by weight, the mechanical strength of the obtained cured product is reduced.

As the reinforcing fibers, those used in ordinary cement products can be used. Such a material is not particularly restricted but includes, for example, polypropylene fiber, vinylon fiber, rayon fiber, alkali-resistant glass fiber, carbon fiber, acrylic fiber, aramid fiber, acrylonitrile fiber and the like. These can be used alone or in combination of two or more.

The reinforcing fibers preferably have a fiber diameter of 1 to 500 μm. If it is less than 1 μm, a fiber ball is formed during mixing, and the strength of the obtained cured product tends to decrease. If it exceeds 500 μm, no reinforcing effect such as improvement in tensile strength is exhibited. The reinforcing fibers preferably have a fiber length of 1 to 15 mm. If it is less than 1 mm, no reinforcing effect such as improvement in tensile strength appears, and
If it exceeds 3, the dispersibility decreases, and a cured product having uniform strength cannot be obtained.

The amount of the reinforcing fibers is SiO ₂ --Al
_It is preferably 10 parts by weight or less based on 100 parts by weight of the ₂ O ₃ -based powder. If the amount exceeds 10 parts by weight, the dispersibility of the reinforcing fibers is reduced.

The pigment is not particularly limited, and examples thereof include metal oxide pigments such as iron oxide, titanium oxide, and cobalt oxide; and carbon black. The amount of the pigment _is preferably 50 parts by weight or less with respect to SiO 2 -Al ₂ O ₃ -based powder 100 parts by weight. If the amount exceeds 50 parts by weight, the hiding power of the obtained cured product surface is not improved, and it is uneconomical.

In the present invention, the method of mixing the respective raw materials is not particularly limited. For example, a method using a mixer such as a paddle rotary mixer, an oscillating mixer, and a screw mixer can be employed. In this case, after the powder raw material and the solid raw material are dry-mixed in advance, the alkali metal silicate aqueous solution may be added and mixed, or all the raw materials may be simultaneously supplied and mixed. After mixing the alkali metal silicate aqueous solution and some of the solid raw materials, other raw materials may be sequentially mixed.

In the present invention, examples of a method for forming irregularities on at least one surface of the cured product include a sand blast, a grinder, a rudder, and a sand blast. Among them, abrasives specified in JIS R 6001 are preferable. If the surface roughness is too fine, the adhesion strength of the laminate is not obtained, and if the surface is too coarse, the quality of the obtained laminate varies, so that the surface roughness (Rmax) is 0.1 to
1 mm is preferred.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below based on examples.

[0044]

【Example】

Example 1 1) SiO ₂ · Al ₂ O ₃ -based powder A Metakaolin powder (trade name “SA” manufactured by Engelhart Co., Ltd.)
TINETONESO33 ”, average particle size 3.3 μm, B
ET specific surface area (5.8 l / g)) 100 parts by weight, 0.5 part by weight of a mixed solution of 25% by weight of triethanolamine and 75% by weight of ethanol were added to an ultra fine mill (zirconia ball, manufactured by Mitsubishi Heavy Industries, Ltd.). 10mm used, ball filling rate 85% by volume), and mechanical energy of 10kwh / kg
To obtain SiO ₂ .Al ₂ O ₃ type powder A. still,
The applied mechanical energy was obtained by dividing the electric power supplied to the ultrafine mill by the unit weight of the treated powder.

The obtained SiO ₂ .Al ₂ O ₃ type powder A1
00 parts by weight, mica (manufactured by Repco, trade name "M-10
0 "), 20 parts by weight, talc (manufactured by Nippon Talc Co., Ltd., 30 parts by weight of trade name" Talc S ", wollastonite (manufactured by Tsuchiya Kaolin Co., Ltd., 57.5 parts by weight of trade name" Kemorit A-60 ", vinylon (Kuraray)) Product name “RM182-
3)) 0.5 parts by weight were supplied to an Erich mixer,
The mixture was dry-mixed for 1 minute to obtain inorganic powder A. To 100 parts by weight of the obtained inorganic powder A, 75 parts by weight of an alkali metal silicate (55% water, 20% SiO ₂ , K ₂
O 25%), 10 parts by weight of aqueous hydrogen peroxide (7% by weight), and 1 part by weight of zinc stearate are added and mixed, and then 320 × 32
It was poured into a 0 × 20 mm formwork until the thickness became 10 mm. After heating the obtained slurry at 50 ° C. for 30 minutes, it was polished with a blast abrasive (trade name “White Morundum WA-30” manufactured by Showa Denko KK). The surface roughness of the obtained foamed cured product was measured using a model “E-RC-S01” manufactured by Tokyo Seimitsu Co., Ltd.
A "was 0.5 mm.

A slurry not containing hydrogen peroxide solution and zinc stearate was poured into the obtained cured product, and the mixture was heated at 85 ° C. for 3 hours.
After curing for a time, a laminate was obtained.

Example 2 The thickness of the cured product was 5 mm, the surface roughness was 0.5 mm, the thickness of the foamed cured product was 10 mm, the surface roughness was 0.5 mm, and a 5 mm cured product layer was further provided thereon. A laminate was obtained in the same manner as in Example 1.

Comparative Example 1 A laminate was obtained in the same manner as in Example 1 except that the foamed cured product was not polished.

Comparative Example 2 A laminate was obtained in the same manner as in Example 2 except that the cured product and the foamed cured product were not polished.

Evaluated bending strength The obtained laminate was cut into 150 × 50 mm and JIS
A three-point bending test with a span of 120 mm was performed in accordance with the above. Cooling / heat repetition test A test was conducted for 10 cycles at 70 ° C. for 8 hours and at -20 ° C. for 16 hours to determine the number of cycles until peeling occurred. The above results are also shown in Table 1.

[0051]

[Table 1]

[0052]

Since the laminate of the present invention has the above-mentioned structure, it has excellent adhesion strength and can easily produce a multilayer laminate.

Claims (1)

[Claims] 1. A method comprising the steps of: forming an irregularity on at least one surface of a cured product obtained by curing a slurry comprising an SiO ₂ —Al ₂ O ₃ -based powder, an alkali metal silicate and water; And curing the laminate.