JP2000282399A - Composite hardened material and composite building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite hardened material excellent in processability and productivity and having high bending strength and useful for building materials, etc., by mixing a fibrous material into an amorphous substance composed of a system of oxides. SOLUTION: This composite hardened material is obtained by mixing 2-75 wt.% fibrous material, e.g. organic fibrous material comprising polysaccharide and further, 0.1-1.2 wt.% halogen such as chlorine, bromine or fluorine into an amorphous substance comprising a system of two or more kinds of oxides selected from Al2O3, SiO2, CaO, Na2O, MgO, P2O5, SO3, K2O, TiO2, MnO, Fe2O3 and ZnO, etc., preferably Al2O3-SiO2-CaO system composed of 5-51 wt.% Al2O3, 8-53 wt.% SiO2 and 10-63 wt.% CaO, forming the resultant composite material and carrying out hardening treatment of the formed material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite cured product that can be used as various industrial materials and a composite building material using the same.

[0002]

2. Description of the Related Art Effective utilization of various industrial wastes has been studied in recent years from the viewpoint of protecting the global environment. For example, in the construction industry, which has consumed a large amount of forest resources until now, new construction materials are required for industrial waste,
In addition to suppressing the consumption of forest resources, the conventional inorganic boards, for example, calcium silicate board, perlite board, slag gypsum board, wood chip cement board, gypsum board, etc., realize low cost and high functionality. Suggestions have been made for it.

For example, Japanese Patent Application Laid-Open No. 7-41350 discloses that pulp residue (scum) generated after the production of paper is effectively used as a building panel. In this technique, an inorganic substance such as silica or alumina obtained by firing a scum is mixed with cement, fiber and water, and pressed against a porous iron plate. Also, Japanese Patent Laid-Open No. 10-21
No. 8643 discloses a cement admixture containing waste molten slag.

[0004]

However, Japanese Patent Application Laid-Open No.
In the technique of Japanese Patent No. 41350, there is a problem in that workability is poor because an iron plate and cement are used, and furthermore, the cement needs to be cured, thereby lowering productivity.

Further, the technique disclosed in Japanese Patent Application Laid-Open No. 10-218643 has a problem that it has excellent compressive strength but low flexural strength. It is necessary to increase the strength.

[0006] Furthermore, since any technique uses cement, nails or the like cannot be hit, and if forcedly hit, there is a disadvantage that cracks may be generated.

Accordingly, the present invention proposes a composite cured product having improved bending strength and a composite building material using the composite cured product, which solves the above-mentioned problems and does not impair workability and productivity. The purpose is to:

[0008]

The gist of the present invention is as follows.
It is as follows. (1) A composite cured product comprising an amorphous material composed of two or more oxides, wherein a fibrous material is mixed in the amorphous material.

(2) In the above (1), the oxide is Al ₂
O ₃ , SiO ₂ , CaO, Na ₂ O, MgO, P ₂ O
_5. A composite cured product characterized by being SO ₃ , K ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ or ZnO.

(3) A composite cured product comprising an Al ₂ O ₃ —SiO ₂ —CaO-based amorphous material, wherein a fibrous material is mixed in the amorphous material.

(4) A composite cured product comprising an Al ₂ O ₃ —SiO ₂ —CaO—oxide-based amorphous material, wherein a fibrous material is mixed in the amorphous material.

(5) In the above (4), the oxide is Na _{2
O, MgO, P 2 O 5} , SO 3, K 2 O, TiO 2, M
A composite cured product, which is at least one selected from nO, Fe ₂ O ₃ and ZnO.

(6) In the above (3) or (4), the amorphous material is converted into Al ₂ O ₃ , SiO ₂ and CaO, respectively, and is based on the total weight of the Al ₂ O ₃ : composite cured product. 5
51% by weight, SiO ₂ : 8 based on the total weight of the composite cured product
To 53% by weight and CaO: a composite cured body characterized in that the composition contains 10 to 63% by weight based on the total weight of the composite cured body and the total of the three does not exceed 100% by weight.

(7) The composite cured product according to any one of the above (1) to (6), wherein the fibrous material is an organic fibrous material comprising a polysaccharide.

(8) The composite cured product according to any one of the above (1) to (7), further comprising a halogen.

(9) The composite cured product according to any one of the above (1) to (8), further comprising a crystal.

[0017]

(10) A composite cured product obtained by curing papermaking sludge, which is industrial waste.

(11) Al, Si, C by X-ray fluorescence analysis
a, the presence of two or more elements selected from Na, Mg, P, S, K, Ti, Mn, Fe and Zn was confirmed;
A composite cured product, characterized in that fibrous substances are mixed in an amorphous material having a halo in the range of 2θ: 15 ° to 40 ° in a line diffraction analysis.

(12) The presence of Al, Si and Ca was confirmed by X-ray fluorescence analysis.
A composite cured product, characterized in that a fibrous material is mixed in an amorphous material in which halo is observed in a range of 15 ° to 40 °.

(13) The presence of Al, Si and Ca was confirmed by X-ray fluorescence analysis, and in addition to these, Na, Mg, P, S, K, Ti, Mn,
The presence of at least one element selected from Fe and Zn was confirmed, and in X-ray diffraction analysis, 2θ: 1
A composite cured product, characterized in that a fibrous material is mixed in an amorphous material in which halo is observed in a range of 5 ° to 40 °.

(14) The composite cured product according to any one of the above (11) to (13), wherein the fibrous substance is an organic fibrous substance comprising a polysaccharide.

(15) The composite cured product according to any one of the above (11) to (14), further comprising a halogen.

(16) The composite cured product according to any one of the above (11) to (15), further comprising a crystal.

(17) The composite cured product according to any one of the above (11) to (16), wherein the amorphous substance is obtained by curing papermaking sludge as industrial waste.

(18) The composite cured product according to any one of the above (1) to (17), further comprising an inorganic powder.

(19) The composite cured product according to any one of the above (1) to (17), further comprising a binder.

(20) A composite cured product according to any one of (1) to (9) or (11) to (17), wherein the fibrous material is oriented. In addition, that the fibrous material is oriented means that the longitudinal direction of each fiber is aligned in a specific direction.

(21) A composite building material in which a reinforcing layer is formed on at least one surface of a core material, wherein the core material is provided with the above (1) to
A composite building material obtained by applying the composite cured product according to any one of (20) to (20).

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The structure of a composite cured product of the present invention
FIG. 1 schematically shows this. The composite cured body 1 basically includes an amorphous body 2 composed of two or more oxides, and a fibrous material 3 mixed in the amorphous body 2. Here, the amorphous body composed of two or more kinds of oxides is an oxide (1) -oxide (2)... -Oxide (n) system (where n
Is a natural number, oxide (1), oxide (2),...
The oxide (n) is an amorphous body of different oxides).

Although it is difficult to accurately define such an amorphous substance, it is difficult to form an amorphous compound by performing a solid solution or hydration reaction of two or more oxides. Conceivable. Such inorganic amorphous compounds are analyzed by fluorescent X-ray analysis to determine the elements (Al, Si,
Ca, Na, Mg, P, S, K, Ti, Mn, Fe, Z
n or more selected from n), and a halo is observed in the range of 2θ: 15 ° to 40 ° in the analysis chart by X-ray diffraction. This halo is a gentle undulation of the intensity of the X-ray, and is observed as a broad swell on the X-ray chart. The halo has a half width of 2θ: 2 ° or more.

In this composite cured product 1, the amorphous material 2 becomes a strength-generating material, and the fibrous material 3 is dispersed in the amorphous material 2 to improve the fracture toughness. Impact resistance can be improved. In addition, a homogeneous cured product having no anisotropy in strength can be obtained. Furthermore, since it is an amorphous body, there is an advantage that sufficient strength can be obtained at a low density.

The reason why the above-mentioned amorphous material becomes a strength-expressing substance is not clear, but it is presumed that it may be because the progress of cracks is inhibited as compared with the crystalline structure. Further, since the fibrous material is more easily dispersed uniformly in the amorphous state than in the crystalline state, it is considered that the fracture toughness value is also improved. As a result, even if a nail is driven or a through hole is provided,
Since cracks do not occur, it is optimal for materials that require processing, such as building materials.

Here, as the oxide, a metal and / or nonmetal oxide can be used, and Al ₂ O ₃ , SiO _{2
2, CaO, Na 2 O,} MgO, P 2 O 5, SO 3, K
It is desirable to be selected from ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ and ZnO. In particular, Al ₂ O ₃ —Si
O ₂ —CaO-based or Al ₂ O ₃ —SiO ₂ —CaO—
The most suitable is an oxide-based amorphous material or a composite of these amorphous materials. The oxide in the latter amorphous body is at least one kind of metal and / or non-metal oxide except Al ₂ O ₃ , SiO ₂ and CaO.

First, the amorphous body made of Al ₂ O ₃ —SiO ₂ —CaO system is made of Al ₂ O ₃ , SiO ₂ and CaO.
Is a compound having an amorphous structure in which all or a part of each component is formed by solid solution or hydration reaction with each other. That is, Al ₂ O ₃ and SiO ₂ , SiO ₂ and Ca
O, Al ₂ O ₃ and CaO, and Al ₂ O ₃ , SiO ₂
It is considered to include any of the compounds formed by causing a solid solution or a hydration reaction or the like with a combination of CaO and CaO. In such an inorganic amorphous compound, Al, Si, and Ca are confirmed by fluorescent X-ray analysis, and a halo is seen in the range of 2θ: 15 ° to 40 ° in an analysis chart by X-ray diffraction. This halo is a gradual undulation of the intensity of the X-ray, and is observed as a broad swell on the X-ray chart. The halo has a half width of 2θ: 2 ° or more.

Further, Al ₂ O ₃ , SiO ₂ and CaO
Other than at least one oxide, ie, Al
_The amorphous body composed of ₂ O ₃ —SiO ₂ —CaO—oxide system includes, in addition to the combination of the above Al ₂ O ₃ —SiO ₂ —CaO system, Al ₂ O ₃ and oxide, and SiO ₂ and oxide , C
aO and oxide, Al ₂ O ₃ and SiO ₂ and oxide, SiO
₂ and CaO and an oxide, Al ₂ O ₃ and CaO and an oxide, or a compound formed by performing a solid solution or hydration reaction with a combination of Al ₂ O ₃ and SiO ₂ and CaO and an oxide. It is considered to include.

It should be noted that the number of oxides is two or more, that is, Al
_Two O_Three -SiO_Two -CaO-oxide (n) type (n is 2 or more)
In the case of the amorphous material of the above (natural number), these oxides, for example,
For example, oxide (1), oxide (2) ... oxide (n)
(N is a natural number of 2 or more, and oxide (n) has a different value of n.
Each means a different oxide, and Al_Two 
O_Three, SiO_Two , Excluding CaO)
Solid solution or hydration counterpart in combination of two or more selected from
Al, a compound produced by the equivalent_Two O_Three , S
iO_Two , CaO is a solid solution in a combination of two or more
Or a compound formed by hydration, etc.
Furthermore, oxide (1), oxide (2) ... oxide (n)
(N is a natural number of 2 or more)
And one kind, Al _Two O_Three , SiO_Two , Selected from CaO
Solid solution or hydration reaction in combination with at least one
Is considered to contain any of the compounds produced by the
available.

Such an inorganic amorphous compound has a fluorescent X
According to the line analysis, in addition to Al, Si and Ca, the elements (Na, Mg, P, S, K, Ti, Mn, F
e, Zn), and a halo is observed in the range of 2θ: 15 ° to 40 ° in the analysis chart by X-ray diffraction. This halo is a gradual undulation of the intensity of the X-ray, and is observed as a broad swell on the X-ray chart. The halo has a half width of 2θ: 2 ° or more.

Here, Al ₂ O ₃ , SiO ₂ and Ca
Oxides to be combined with O are one kind or two or more kinds, and are metals other than Al ₂ O ₃ , SiO ₂ and CaO and / or
Alternatively, non-metal oxides can be used, such as Na ₂ O, M
gO, P ₂ O ₅ , SO ₃ , K ₂ O, TiO ₂ , MnO,
It can be selected from Fe ₂ O ₃ and ZnO. This selection can be made based on the characteristics expected of the composite cured product.

For example, since Na ₂ O or K ₂ O can be removed with an alkali or the like, if the removal treatment is performed prior to the plating treatment, the surface to be plated on the surface of the composite hardened body becomes rough and acts as an anchor for plating. be able to. Mg
O forms a solid solution with Al ₂ O ₃ , SiO ₂ , and CaO to contribute to strength development, and greatly improves bending strength and impact resistance. P
₂ O ₅ is particularly advantageous when used for biomaterials (artificial roots, artificial bones) to aid adhesion with bone. SO ₃
Has a bactericidal action and is suitable for antibacterial building materials. TiO
₂ is a white colorant and also acts as a photo-oxidation catalyst, so it can forcibly oxidize attached organic pollutants and can be cleaned only by irradiating light. Has a unique effect that it can be used as a reaction catalyst. MnO is useful as a dark colorant, Fe ₂ O ₃ is useful as a light colorant, and ZnO is useful as a white colorant. In addition, these oxides
Each may exist alone in the amorphous body.

The composition of the above-mentioned amorphous body was Al ₂ O
₃ , in terms of SiO ₂ and CaO, Al ₂ O ₃ : 5 to 51% by weight based on the total weight of the composite cured product, SiO ₂ :
8 to 53% by weight based on the total weight of the composite cured product and Ca
O: 10 to 63% by weight based on the total weight of the composite cured product,
And it is preferable to contain them in a range where the total does not exceed 100% by weight.

The reason is that the content of Al ₂ O ₃ is 5% by weight.
If the content is less than 50% or more than 51% by weight, the strength of the composite cured product will be reduced, and if the content of SiO ₂ is less than 8% by weight or more than 53% by weight, the strength of the composite cured product will be reduced. In addition, the content of CaO is less than 10% by weight or 6%.
Even when the amount exceeds 3% by weight, the strength of the composite cured product is still lowered.

Further, in terms of oxide, CaO / SiO
Adjusting the ratio of ₂ to 0.2 to 7.9 and the ratio of CaO / Al ₂ O ₃ to 0.2 to 12.5 is advantageous for obtaining a cured product having high strength.

Further, Al ₂ O ₃ , SiO ₂ and CaO
Oxides other than Na ₂ O, MgO, P ₂ O ₅ , S
O ₃ , K ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ and Z
When one or more of nO is contained, the preferred content of each component is as follows. It goes without saying that the total amount of these oxides does not exceed 100% by weight. Na ₂ O: 0.1 to 1.2% by weight based on the total weight of the composite cured body MgO: 0.3 to 11.0% by weight based on the total weight of the composite cured body P ₂ O ₅ : Composite cured body 0.1 to 3.5% by weight based on the total weight of the composite cured product SO ₃ : 0.1 to 3.5% by weight based on the total weight of the composite cured product K ₂ O: 0 based on the total weight of the composite cured product .1～1.2 wt% TiO _2: from 0.1 to 8.7 wt% MnO, relative to the total weight of the composite hardened product: 0.1 to 1.5 wt% Fe with respect to the total weight of the composite cured body ₂ O ₃ : 0.2 to 17.8% by weight based on the total weight of the composite cured body ZnO: 0.1 to 1.8% by weight based on the total weight of the composite cured body The reason for limiting the range is that if the ratio is outside the above range, the strength of the composite cured body is reduced.

It should be noted that whether or not the structure is amorphous can be confirmed by X-ray diffraction. That is, 2θ: 15 ° by X-ray diffraction
If a halo is observed in the region of ４０40 °, it can be confirmed that it has an amorphous structure. In the present invention, in addition to the completely amorphous structure, the amorphous structure may have a crystal, specifically, Hydrogen Alu
minium Silicate, Kaolinite, Zeolite, Gehlenite,
syn, Anorthite, Melitite, Gehlenite-synthetic,
tobermorite, xonotlite, and ettringite, SiO _2,
Al ₂ O ₃ , CaO, Na ₂ O, MgO, P ₂ O ₅ , S
O ₃ , K ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ and Z
An oxide such as nO may be mixed.

Although it is not considered that these crystals themselves become a strength-expressing substance, if they have effects such as increasing the hardness and density to improve the compressive strength and suppressing the progress of cracks. Conceivable. The content of the crystal is desirably 0.1 to 50% by weight based on the total weight of the composite cured product. This is because if the number of crystals is too small, the above effect cannot be obtained, and if the number is too large, the strength is reduced.

Incidentally, the above Al ₂ O ₃ —SiO ₂ type crystalline compound is manufactured by Hydrogen Aluminum Silicate, Kaolini.
te, Zeolite, Al ₂ O ₃ —CaO based crystalline compounds are Calcium Aluminate, CaO—SiO ₂ based crystalline compounds are Calcium Silicate, Al ₂ O ₃ —SiO ₂ —Ca
O-type crystalline compounds are Gehlenite, syn and Anorthite, and Al ₂ O ₃ —SiO ₂ —CaO—MgO-type crystalline compounds are Melitite and Gehlenite-synthetic.

Further, a crystal containing Ca is desired.
Best, Gehlenite, syn (Ca_Two Al_Two O₇ ), Meliti
te-synthetic (Ca_Two (Mg_0.5 Al_0.5 ) (Si_1.5 
Al _0.5 O₇ )), Gehlenite-synthetic (Ca_Two (M
g_0.25Al_0.75) (Si_1.25Al_0.75O₇ )), Anorth
ite, ordered (Ca_Two Al_Two Si_Two O₈ ) 、 Carbon carbonate
(Calcite) may be contained.

In the composite cured product of the present invention, a halogen may be added to an amorphous material composed of two or more oxides. The halogen serves as a catalyst for a solid solution or hydrate formation reaction and also acts as a combustion suppressing substance. Its content is desirably 0.1 to 1.2% by weight. This is because if it is less than 0.1% by weight, the strength is low, and if it exceeds 1.2% by weight, harmful substances are generated by combustion. As the halogen, chlorine, bromine and fluorine are desirable.

Similarly, calcium carbonate (Calcite) may be added. Calcium carbonate itself is not a strength-expressing substance, but it is thought that by surrounding the calcium carbonate with an amorphous body, it contributes to strength improvement by actions such as inhibiting the progress of cracks. The content of the calcium carbonate is 48 to the total weight of the composite cured product.
% By weight or less is desirable. The reason for this is that if it exceeds 48% by weight, the bending strength is reduced. Further, the content is desirably 0.1% by weight or more. If the content is less than 0.1% by weight, it does not contribute to the improvement in strength.

Further, the addition of a binder is advantageous for further improving the strength and for improving the water resistance, chemical resistance and fire resistance. The binder desirably comprises one or both of a thermosetting resin and an inorganic binder. As thermosetting resins, phenolic resins,
At least one resin selected from melamine resin, epoxy resin and urea resin is desirable. The inorganic binder is preferably at least one selected from the group consisting of sodium silicate, silica gel and alumina sol. Note that a thermosetting resin, for example, at least one thermosetting resin selected from a phenol resin, a melamine resin, an epoxy resin, a urea resin, and a urethane resin may be applied to the surface.

Next, in the present invention, a mixture in the amorphous body
The fibrous material to be used may be either organic or inorganic.
No. Organic fibrous materials include vinylon and polypropylene
Synthetic fibers such as polyethylene and polyethylene, and polysaccharides
At least one selected from organic fibrous materials comprising
Can be used, but is an organic fibrous material consisting of polysaccharides
It is desirable. Because polysaccharides have OH groups
And the hydrogen bond causes Al _Two O_Three , SiO_Two Or CaO
It is because it is easy to bond with various compounds of the above.

The polysaccharide is preferably at least one compound selected from amino sugars, uronic acids, starch, glycogen, inulin, lichenin, cellulose, chitin, chitosan, hemicellulose and pectin. As the organic fibrous material composed of these polysaccharides, pulp, pulp grounds, and crushed waste paper such as newspapers and magazines are advantageously suited. The pulp contains about 10 to 30% by weight of lignin in addition to cellulose.

On the other hand, as the inorganic fibrous material, at least one selected from alumina whiskers, SiC whiskers, silica-alumina ceramic fibers, glass fibers, carbon fibers, and metal fibers can be used.

The content of the fibrous material is 2 to 75.
% By weight. The reason for this is that if the content is less than 2% by weight, the strength of the composite cured product is reduced, while if it exceeds 75% by weight, the fire protection performance, water resistance, dimensional stability and the like may be reduced. Further, the average length of the fibrous material is desirably 10 to 3000 μm. If the average length is too short, no entanglement occurs, and if the average length is too long, voids are formed, and the strength of the inorganic cured product tends to decrease.

It is recommended that the above-mentioned composite cured product is obtained by drying and coagulating and hardening industrial waste, and particularly, the one obtained by drying and coagulating and hardening papermaking sludge (scum) is optimal. That is, the papermaking sludge is a pulp residue containing an inorganic substance, is low in cost because industrial waste is used as a raw material, and contributes to solving environmental problems. Moreover, the papermaking sludge itself has a function as a binder, and has an advantage that it can be formed into a desired shape by kneading with other industrial waste.

In the papermaking sludge, besides pulp, Al ₂ O ₃ , SiO ₂ , CaO, Na ₂ O, Mg
O, P ₂ O ₅ , SO ₃ , K ₂ O, TiO ₂ , MnO, F
It generally contains a crystal of e ₂ O ₃ and ZnO or a sol that is a precursor of these oxides, or a composite thereof, at least one selected from halogen and calcium carbonate, and water. In particular, waste paper of high quality paper contains a large amount of calcium-based crystals such as kaolin and calcium carbonate. Therefore, paper sludge containing a large amount of waste paper is suitable.

The water content in the papermaking sludge is from 20 to
Desirably, it is 80% by weight. This is because if the water content is less than 20% by weight, it becomes too hard and molding becomes difficult, while if it exceeds 80% by weight, it becomes a slurry and molding becomes difficult.

Here, as shown in FIG.
It is advantageous to mix the inorganic powder 4 therein to improve the fire resistance or to improve the strength by reacting with the amorphous body to form a strength-expressing substance, thereby adjusting the amount of the inorganic powder. By doing so, the specific gravity of the composite cured product can also be adjusted.

As the inorganic powder, calcium carbonate, calcium hydroxide, shirasu, shirasu balloon, perlite,
At least one selected from aluminum hydroxide, silica, alumina, talc, calcium carbonate, and industrial waste powder
Seeds can be used. In particular, as the industrial waste powder, it is desirable to use at least one type of industrial waste powder selected from calcined powder of papermaking sludge, grinding dust of glass, and crushed silica sand. This is because by using these industrial waste powders, cost reduction can be realized and furthermore, it can contribute to solving environmental problems.

The inorganic powder obtained by firing papermaking sludge can be obtained by subjecting papermaking sludge to heat treatment at 300 to 1500 ° C. The inorganic powder thus obtained is
Since it is amorphous, has excellent strength and toughness, and has a low density, it can be reduced in weight by being dispersed in a composite cured product. In addition, the papermaking sludge is kept at 300 ° C or more and 800 ° C or more.
The inorganic powder obtained by sintering at a temperature less than or less than 300 ° C. and then quenching after the heat treatment at 300 to 1500 ° C. is advantageous because it surely contains an amorphous body. The inorganic powder desirably has a specific surface area of 0.8 to 100 m ² / g. If it is less than 0.8 m ² / g, the contact area between the amorphous body and the inorganic powder becomes small and the strength is reduced.
If it exceeds m ² / g, effects such as crack development and improvement in hardness are reduced, and as a result, strength is reduced.

Further, it is desirable that the inorganic powder contains at least one inorganic substance selected from silica, alumina, iron oxide, calcium oxide, magnesium oxide, potassium oxide, sodium oxide and phosphorus pentoxide. These are chemically stable, have excellent weather resistance, and have desirable characteristics as industrial materials such as building materials.

If the average particle size of the inorganic powder is too small or too large, sufficient strength cannot be obtained.
It is desirable to be in the range of 100 μm. The content of the inorganic powder is desirably 10 to 90% by weight. That is, if the amount of the inorganic powder is too large, the strength is reduced, and if the amount of the inorganic powder is too large, the strength is reduced, and in any case, the strength is reduced.

The composite cured product according to the present invention is used in various industries, and is used as a medical material for artificial limbs, artificial bones and artificial roots, including new building materials replacing calcium silicate plates, perlite boards, plywood, gypsum boards, and the like. It can be used for electronic materials such as materials, core substrates of printed wiring boards, and interlayer resin insulation layers.

Therefore, a composite building material will be described below as one application example of the composite cured body. That is,
As shown in FIG. 3, in a composite building material in which a reinforcing layer 6 is formed on at least one surface of the core material 5 and on both surfaces in the illustrated example, the composite cured body 1 of the present invention is applied to the core material 5. It is characterized by the following. That is, by using the core material 5 as the composite cured body 1 of the present invention, even when a tensile force is applied to the core material, the core material itself has excellent bending strength, and furthermore, a reinforcing layer is formed on the surface of the core material. Is provided, so that it is not easily broken.
Further, even when pressure is locally applied to the surface, no dent or dent occurs.

Further, the composite building material of the present invention is provided with a decorative layer such as a coating, a decorative panel and a decorative veneer on the reinforcing layer 6 upon use thereof, so that the impact resistance is improved. Scratches such as dents are less likely to occur, and the decorative surface is not distorted by the scratches and the design is not degraded.

The reinforcing layer 6 has a structure in which the fiber base material 6b is embedded in the resin 6a. It is particularly desirable to use a thermosetting resin for the resin 6a. That is, unlike a thermoplastic resin, a thermosetting resin has excellent fire resistance and does not soften even at a high temperature, so that the function as a reinforcing layer is not lost. As the thermosetting resin, a phenol resin, a memelamine resin, an epoxy resin, a polyimide resin, a urea resin and the like are suitable. In order to impart sufficient rigidity, impact resistance, and even higher fire resistance to the reinforcing layer, the content of the thermosetting resin in the reinforcing layer is desirably in the range of 10% by weight to 65% by weight.

On the other hand, it is desirable to use inorganic fibers for the fiber base 6b. This is because the strength of the reinforcing layer 6 can be improved and the coefficient of thermal expansion can be reduced. It is preferable to use glass fiber, rock wool, and ceramic fiber as the inorganic fiber because they are low in cost and have excellent heat resistance and strength. This fiber base material is a material obtained by molding a discontinuous fiber into a mat shape, or a material obtained by cutting continuous long fibers into a mat shape by cutting into 3 to 7 cm (a so-called chopped strand mat), and dispersing in water to form a sheet. A material obtained by piling up, a continuous long fiber spirally laminated to form a mat, or a continuous long fiber woven is applicable.

Further, the thickness of the reinforcing layer is from 0.2 mm to
It is desirable to be 3.5 mm. This is because, if it is set in this range, sufficient rigidity and impact resistance can be obtained, and high workability can be maintained. The reinforcing layer may contain a flame retardant such as aluminum hydroxide and magnesium hydroxide, and a commonly used inorganic binder such as silica sol, alumina sol, and water glass.

The method for producing the composite cured product and the composite building material of the present invention will be described below. First, a method for producing a composite cured product is as follows. That is, papermaking sludge is used as a raw material of the composite cured product. Papermaking sludge includes printing and information paper, kraft paper, titanium paper,
It is desirable to use papermaking sludge discharged when making tissue paper, dust paper, toilet paper, sanitary products, towel paper, industrial hybrid paper, and household hybrid paper. As the commercially available papermaking sludge, "cyclone ash", "raw sludge", etc., which are handled by Maruto Kiln Co., Ltd. can be used.

This papermaking sludge is poured into a desired formwork, or into a formwork provided with a filter, and then pressed to remove water, or a method of forming a papermaking sludge slurry. Perform molding. Then, after molding, drying and curing at a heating temperature of 20 to 160 ° C. yields a composite cured product. If the heating temperature is too high, deformation or cracks may occur, while if it is too low, a long time is required for drying and the productivity is reduced.

In particular, in order to form the composite cured product into a plate shape,
While conveying the paper sludge in a conveyor, and the sheet-like shaped body pressed by the roll, and pressing while heating the formed sheet at a heating temperature of 80 to 160 ° C., forming a plate-shaped core material. An appropriate pressure at that time is 1 to 20 kgf / cm ² . Further, the inorganic powder can be dispersed in the composite cured product by adding and mixing the inorganic powder to the papermaking sludge, followed by heating and curing.

In addition to the papermaking sludge, metal alkoxides and metal hydroxides can be used as raw materials. For example, a mixture of alkoxides or hydroxides of Al, Si, and Ca and a crushed product of used paper are mixed, and the mixture is hydrolyzed and polymerized in the presence of an acid or alkali to form a sol. You may make it gel. Such gels result in Al ₂ O ₃ , SiO ₂ , Ca
O, Na ₂ O, MgO, P ₂ O ₅ , SO ₃ , K ₂ O, T
It is presumed to be the same as a compound obtained by solid solution or hydration reaction of an oxide such as iO ₂ , MnO, Fe ₂ O ₃ and ZnO.

Incidentally, there are various techniques using papermaking sludge, but all of them have different technical contents from the present invention. That is, JP-A-49-86438 discloses that
A hot-pressed mixture of pulp scum (cellulose component) and lime scum is disclosed, but pulp scum means cellulose and uses the inorganic component in papermaking sludge as in the present invention. However, it is not a dispersion of fibers in inorganic amorphous. For this reason, fracture at the grain boundaries of limescale or crack propagation cannot be prevented, and problems remain in bending strength and compressive strength. Moreover, the limescale is
Crystalline substance (calcium oxide) burned from paper pulp
Which is clearly distinguished from the amorphous body of the present invention.

Further, JP-A-7-47537 and JP-A-7-6
9701, 6-293546 and 5-270
No. 872 discloses a technique of combining cement and inorganic reinforcing fibers, and JP-A-10-15923 discloses a technique of mixing pulp sludge with crystalline gypsum.
Japanese Patent Application Laid-Open No. 9-2880 discloses a technique which focuses only on fibers in pulp waste, and Japanese Patent Application Laid-Open No. 53-81388 discloses a fiber in pulp waste (20% fiber, 0.01% earth and sand).
Each of the techniques described above is different from a technique in which a fibrous substance is dispersed in an inorganic amorphous material as in the present invention.

Furthermore, Japanese Patent Application Laid-Open No. 51-30088 describes a technique for forming baked ash of pulp waste and a lightweight inorganic material, but does not describe calcination conditions and the like. Cannot be obtained. JP-A-8-2
No. 46400 discloses a technique in which waste paper pulp itself is used instead of papermaking sludge. JP-A-48-443
No. 49 discloses a technique in which a pulp waste containing an organic substance and an inorganic substance is mixed with a polymer emulsion or the like. The term "inorganic" refers to silicon oxide, aluminum oxide and iron oxide. And two or more metal oxides as in the present invention are different from those constituting a complex amorphous system. And

The composite building material is manufactured as follows. First, the papermaking sludge is formed into a sheet by a known method such as circular web forming, fourdrinier forming, dewatering press, and extrusion forming, and then dried, or the mixture is conveyed on a conveyor and pressed with a roll to form a sheet-like molded product. It is dried after molding. On the other hand, the fiber base material is impregnated with a resin, heated at 25 to 70 ° C., and dried to obtain a reinforcing sheet. Next, the sheet-shaped molded body and the reinforcing sheet are laminated, and pressed while heating,
It is molded into a composite building material consisting of a core material (composite cured body) and a reinforcing layer. It is appropriate that the heating temperature here is 80 to 200 ° C. and the pressure is about 1 to ²⁰ kgf / cm ² . Here, the term “pressing” refers to maintaining the pressure applied. By this pressing, the fibrous material can be oriented to increase the bending strength, and since water can be removed by applying pressure, it is possible to prevent water from being taken in and excessively progressing crystallization.

Instead of the above method, the resin composition was impregnated into a mat of inorganic fibers, dried, and then heated and pressed.
A method may be used in which a thermosetting resin is cured and molded to form a reinforcing layer, and the reinforcing layer is attached to a core material that has been cured in advance with an adhesive.

Further, the surface of glass fiber, rock wool, or ceramic fiber is coated with a thermosetting resin such as a phenol resin in another configuration, and a fiber base made of these fibers is laminated on a sheet-like molded body. And hot pressing. This method of coating the fiber surface with a thermosetting resin in a separate step is advantageous because the adhesion to the impregnated resin is improved, the fibers are easily bonded to each other, and the resin impregnation rate can be further improved. .
Examples of such a coating method include a method in which the fiber base material is impregnated with an uncured thermosetting resin and dried, or a method in which a raw material melt of glass fiber, rock wool, and ceramic fiber flows out of a nozzle and is blown. Alternatively, there is a method in which fibers are formed by a centrifugal method, and a solution of a thermosetting resin such as a phenol resin is sprayed simultaneously with the formation of the fibers.

When glass fiber, rock wool, or ceramic fiber is used as the constituent material of the fiber base material, it is preferable to coat a silane coupling agent. The surface of the composite building material obtained in this way,
The back surface can be painted, or a decorative plate or a decorative veneer can be attached with an adhesive or the like. The coating is performed by printing and spraying various pigments, inks, and the like. The decorative board is a three-layer decorative board including a phenol resin-impregnated core layer, a melamine resin-impregnated pattern layer, and a melamine resin-impregnated overlay layer, a melamine resin-impregnated backer layer, a phenol resin-impregnated core layer, and a melamine resin-impregnated pattern layer. And a decorative plate having a four-layer structure composed of an overlay layer impregnated with a melamine resin. In particular, in the case of a decorative board having a phenolic resin-impregnated core layer as the core layer, the surface strength is significantly increased, so that it can be applied to flooring materials and the like. In addition, high quality wood such as cedar and cypress can be used as the decorative veneer.

[0081]

EXAMPLES (Example 1) Unfired papermaking sludge ("raw sludge" handled by Maruto Kiln Co., Ltd .: solid content 34% by weight, moisture 66)
1512 g). Next, a sheet-like molded product having a thickness of 10 mm was formed while applying a pressure of 3 kgf / cm ² while conveying the papermaking sludge by a conveyor. This sheet-like molded body was heated at 100 ° C. to obtain a plate-shaped composite cured body.

When the composite cured product thus obtained was analyzed using an X-ray fluorescence analyzer (RIX2100, manufactured by Rigaku), it was found that the composition was as follows, in terms of oxide.
The pulp was calcined at 1100 ° C. and measured from the weight loss. Serial Pulp: 51.4 wt%, MgO: 1.4 wt% SiO _2: 24.2 wt%, SO _3: 0.5 wt% Al ₂ O _3: 14.0 wt%, P ₂ O _5: 0 .2 wt% CaO: 8.0 wt%, Cl: 0.2% by weight TiO _2: 1.0 wt%, ZnO: 0.1 wt% Others traces Incidentally, an optical microscope (50 times the side of the composite cured body As a result, the fibers were oriented in a direction perpendicular to the pressing direction.

Example 2 Unsintered papermaking sludge (“raw sludge” handled by Maruto Kiln Co., Ltd., solid content 34% by weight, moisture 6)
(6% by weight) was prepared. Next, the papermaking sludge was conveyed by a conveyor, and a pressure of 3 kgf / cm ² was applied to form a sheet-shaped molded product having a thickness of 10 mm. This sheet-like molded body was heated at 100 ° C. to obtain a plate-shaped composite cured body.

When the thus obtained composite cured product was analyzed using an X-ray fluorescence analyzer (RIX2100 manufactured by Rigaku), it was found that the composition was as follows in terms of oxide. The pulp was calcined at 1100 ° C. and measured from the weight loss. Serial Pulp: 46.0 wt%, TiO _2: 1.0 wt% Al ₂ O _3: 14.0 wt%, SO _3: 1.0 wt% Al ₂ O _3: 14.0 wt%, SO _3: 1.0 wt% CaO: 8.0 wt%, P ₂ O _5: 0.2% by weight Na ₂ O: 0.2 wt%, Cl: 0.3% by weight K ₂ O: 0.2 wt%, Others: Trace amount of Fe ₂ O ₃ : 0.2% by weight,

Example 3 103 parts by weight of a fired papermaking sludge ("Cyclone Ash" handled by Maruto Kiln Co., Ltd.) and 1209 parts by weight of the unfired papermaking sludge of Example 1 were kneaded. The composition of the calcined sludge was analyzed using an X-ray fluorescence analyzer (RIX2100 manufactured by Rigaku) and converted into oxides as follows. (Burned material of paper sludge) SiO ₂ 34.1 wt% MgO 6.0 wt% Al ₂ O ₃ 20.7 wt% P ₂ O ₅ 2.7 wt% Fe ₂ O ₃ 12.4 wt% TiO ₂ 1 2.0% by weight CaO 21.3% by weight SO ₃ 0.5% by weight Cl 0.2% by weight ZnO 0.1% by weight Other trace amount Average particle diameter: 11.0 μm, true specific gravity: 2.756
And specific surface area: 19.0 m ² / g.

Then, while conveying the kneaded material by a conveyor, a pressure of 3 kgf / cm ² was applied, and a thickness of 10 m
m in the form of a sheet. This sheet-like molded body is
By heating at 0 ° C., a plate-shaped composite cured product was obtained.

Example 4 After a sheet-like glass fiber was impregnated with a phenol resin solution obtained by adding a curing agent (impregnation amount: 45% in terms of solid content), it was dried at a temperature of 80 ° C. for 20 minutes to obtain a reinforcing sheet. Obtained. Further, a phenol resin was applied to the front and back surfaces of the core material and dried at a temperature of 80 ° C. for 20 minutes.

Next, a sheet-like molded body was formed in the same manner as in Example 2. Then, the reinforcing sheet is placed on the front and back surfaces of the sheet-shaped molded body, and a pressure of 7 kg is applied at a temperature of 110 ° C.
Press for 20 minutes at f / cm ² , 1mm thick on both sides
A composite building material comprising a reinforcing layer and a core material having a thickness of 10 mm was manufactured. Further, a decorative veneer of cedar board having a thickness of 0.2 mm was attached to the surface of the composite building material via a vinyl acetate adhesive.

Example 5 1512 parts by weight of the unsintered papermaking sludge of Example 1 and 378 parts by weight of a phenol resin were kneaded to obtain a kneaded product. The resulting kneaded material was conveyed by a conveyor, and a pressure of 3 kgf / cm ² was applied to form a 10 mm-thick sheet-like molded product. This sheet-shaped molded body was heated at 110 ° C. to obtain a plate-shaped composite cured body.

Example 6 1200 parts by weight of the unfired papermaking sludge of Example 1, 600 parts by weight of a phenolic resin and 600 parts by weight of a fired papermaking sludge ("Cyclone Ash" handled by Maruto Kiln Co., Ltd.) are kneaded. A kneaded product was obtained. The kneaded product was formed into a sheet having a thickness of 10 mm while being pressed by a pressure of 3 kgf / cm ² while being conveyed by a conveyor.
This sheet-shaped molded body was heated at 110 ° C. to obtain a plate-shaped composite cured body.

(Example 7) A phenol resin (HP-3 manufactured by Asahi Organic Materials Co., Ltd.) was applied to the surface of the composite cured product of Example 1.
000 A) was applied at 100 g / m ² and dried at a temperature of 80 ° C. for 20 minutes. Then, the composite cured product of Example 1 and the cured product treated with the above phenol resin (Example 7) were immersed in water for 24 hours, and the bending strength was measured. In Example 1, it was 137 kgf / cm ² , and in Example 7, it was 295 kgf / cm ² . That is, it was found that the moisture absorption resistance can be improved by applying the resin.

(Embodiment 8) Basically the same as Embodiment 1, except that water is added to papermaking sludge to obtain a solid content of 15% by weight.
And while conveying 1500 kg of this slurry by a conveyor, 63 kgf / cm ² by a dehydration press method.
A pressure of (6.17 MPa) was applied to obtain a 10 mm thick sheet-like molded body. Next, this sheet-like molded body was
It was dried by heating at 00 ° C. to obtain a composite cured product.

Example 9 Basically the same as Example 2, except that water was added to papermaking sludge to obtain a solid content of 20% by weight.
, And 3000 kg of this slurry was conveyed on a conveyor, and was subjected to a dewatering press method at 52 kgf / cm ^2.
A pressure of (5.10 MPa) was applied to form a 10 mm thick sheet-like molded body. Next, this sheet-shaped molded product # 1
It was dried by heating at 00 ° C. to obtain a composite cured product.

Example 10 Basically the same as Example 3, but 103 parts by weight of the fired papermaking sludge, 1800 parts by weight of the unfired papermaking sludge of Example 1 and 4500 parts by weight of water Was kneaded to form a slurry. Then
This slurry is subjected to a dewatering press method at 25 kgf / cm ^2.
A pressure of (2.45 MPa) was applied to obtain a 10 mm thick sheet-like molded body. Next, this sheet-like molded body was
It was dried by heating at 00 ° C. to obtain a composite cured product.

(Embodiment 11) Basically, it is the same as the embodiment 5, but the unsintered papermaking sludge 1800 of the embodiment 1
Parts by weight, 250 parts by weight of phenol resin and 4500 parts of water
By weight and kneaded to obtain a slurry. Next, this slurry was subjected to a dehydration press method at 20 kgf / cm ² (1.96).
By applying a pressure of MPa), a sheet-like molded body having a thickness of 20 mm was obtained. Next, the sheet-shaped molded body was dried by heating at 110 ° C. to obtain a composite cured body.

(Comparative Example 1) 60 parts by weight of calcined scum, water 3
6 parts by weight, 100 parts by weight of cement and 0.3 parts by weight of vinylon fiber were mixed with a forced stirring mixer for 3 minutes to prepare a slurry.
After pressurizing at kgf / cm ² , the mold was released.

(Comparative Example 2) Lime-based sewage sludge molten slag (a product of the Osaka City Sewerage Corporation, whose main chemical component is as follows) was pulverized by a ball mill, and the fineness was 0.35 m in specific surface area.
95 parts by weight of ordinary Portland cement "Chichibu Onoda Co., Ltd." was mixed with 5 parts by weight of a pulverized mixture to give a ² / g (plain value of 3500 cm ² / g), and the SO ₃ content in the cement was 2% by weight. The mixture was adjusted with natural gypsum so as to obtain a mixed cement composition. The cement and sand were mixed at a ratio of 1: 3 and left for 3 days.

SiO ₂ : 33.4% by weight, MgO: 2.4% by weight Al ₂ O ₃ : 14.2% by weight, P ₂ O ₅ : 7.0% by weight Fe ₂ O ₃ : 5.0% by weight %, NaO: 0.7% by weight CaO: 33.9% by weight, K ₂ O: 0.7% by weight

The cured composites and composite building materials obtained in the above Examples and Comparative Examples were tested for flexural strength, compressive strength, workability, and nailability. Table 1 shows the results. The test method was such that the bending strength was JI
S A6901, and the compression strength is JIS A 541
The measurement was performed according to the method specified in No. 6. The workability was determined by cutting using a circular saw for woodworking. Furthermore, regarding nailing properties, the diameter was 4 m.
A nail having a length of 50 mm and a length of 50 mm was hit, and the penetration depth of the nail and the presence or absence of cracks were examined.

[0100]

[Table 1]

The crystal structures of the composite cured products of Examples 1 and 3 were confirmed by X-ray diffraction. The X-ray diffraction charts are shown in FIGS. 4 and 5, respectively. For X-ray diffraction, use Rigaku MiniFlex,
Cu was targeted. A gentle undulation (halo) is observed around 2θ: 22 °, and a peak indicating a crystal structure is also observed, indicating that the crystal structure is mixed in the amorphous structure. From the peak, crystals of calcium carbonate (Calsite), crystals of Kaolinite and SiO ₂ were identified. The content of calcium carbonate was 9.8% by weight based on the composite cured product in terms of a converted value.

[0102]

As described above, the composite cured product of the present invention is an inexpensive material having excellent workability and productivity, and having high bending strength, so that it can be advantageously applied in various fields. It is possible to provide a material optimal for a building material at a low cost, since it is possible to drive a nail in particular.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a composite cured product of the present invention.

FIG. 2 is a schematic cross-sectional view of a composite cured product of the present invention.

FIG. 3 is a schematic sectional view of the composite building material of the present invention.

FIG. 4 is a chart of X-ray diffraction of a composite cured product of Example 1.

FIG. 5 is an X-ray diffraction chart of the composite cured product of Example 3.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Composite hardened body 2 Amorphous body 3 Fibrous material 4 Inorganic powder 5 Core material 6 Reinforcement layer

Continued on the front page (72) Inventor Kenji Sato 1- 1 north of Ibigawa-cho, Ibi-gun, Gifu Prefecture Inside the Ogaki-Kita Plant (72) Inventor Toshihiro Nomura 1- 1 north of Ibigawa-cho, Ibi-gun, Gifu Ibiden Co., Ltd. F-term in the Ogaki Kita Factory (reference) 2E162 CE08 EA18 FA05 FA09 FA14 FA19 FA20 FB07 FC01 FC02 FD06 4F100 AA00A AA00H AA05A AA09A AA17A AA19A AA20A AA21A AA23A AJ03A AT00B AT00C BA01 BA02 BA03A01 BA01 BA02 BA01 BA01 JA20A JK04 JL01 JL02 JL16A YY00A 4L055 AA20 AF09 AG06 AG08 AG15 AG16 AG17 AG18 AG19 AG20 AG79 AG94 AH01 AH37 AJ01 AJ02 BE08 BE14 BF02 BF04 BG04 EA32 FA13 FA19 FA30 GA24

Claims (21)

[Claims] 1. A composite cured product comprising an amorphous material comprising two or more oxides, wherein a fibrous material is mixed in the amorphous material. 2. The method according to claim 1, wherein the oxide is Al ₂ O.
₃ , SiO ₂ , CaO, Na ₂ O, MgO, P ₂ O ₅ ,
A composite cured product comprising SO ₃ , K ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ or ZnO. 3. A composite cured product comprising an Al ₂ O ₃ —SiO ₂ —CaO-based amorphous material, wherein a fibrous material is mixed in the amorphous material. 4. A composite cured product comprising an Al ₂ O ₃ —SiO ₂ —CaO—oxide-based amorphous material, wherein a fibrous material is mixed in the amorphous material. 5. The method according to claim 4, wherein the oxide is Na._Two O,
MgO, P_Two O_Five , SO _Three , K_Two O, TiO_Two , Mn
O, Fe_Two O_Three And at least one selected from ZnO
A composite cured product, which is a seed. 6. The method according to claim 3 or 4, amorphous body, in terms of Al ₂ O _3, SiO ₂ and CaO, respectively, Al ₂ O _3: relative to the total weight of the composite hardened product 5-5
1% by weight, SiO ₂ : 8 to 8% based on the total weight of the composite cured product
53% by weight and CaO: a composite cured body characterized in that the composition contains 10 to 63% by weight based on the total weight of the composite cured body and the total of the three does not exceed 100% by weight. 7. The method according to claim 1, wherein
A composite cured product, wherein the fibrous material is an organic fibrous material comprising a polysaccharide. 8. The method according to claim 1, wherein
A composite cured product further comprising a halogen. 9. The method according to claim 1, wherein
A composite cured product further comprising a crystal. 10. A composite cured product obtained by curing papermaking sludge as industrial waste. 11. Al, Si, C by X-ray fluorescence analysis
a, the presence of two or more elements selected from Na, Mg, P, S, K, Ti, Mn, Fe and Zn was confirmed;
A composite cured product, characterized in that fibrous substances are mixed in an amorphous material having a halo in the range of 2θ: 15 ° to 40 ° in a line diffraction analysis. 12. X-ray fluorescence analysis confirms the presence of Al, Si and Ca, and in X-ray diffraction analysis, 2θ:
A composite cured product, characterized in that a fibrous material is mixed in an amorphous material in which halo is observed in a range of 15 ° to 40 °. 13. X-ray fluorescence analysis confirms the presence of Al, Si and Ca, and in addition to these, Na, Mg, P, S, K, Ti, Mn,
The presence of at least one element selected from Fe and Zn was confirmed, and in X-ray diffraction analysis, 2θ: 1
A composite cured product, characterized in that a fibrous material is mixed in an amorphous material in which halo is observed in a range of 5 ° to 40 °. 14. The composite cured product according to claim 11, wherein the fibrous material is an organic fibrous material comprising a polysaccharide. 15. The composite cured product according to claim 11, further comprising a halogen. 16. The composite cured product according to claim 11, further comprising a crystal. 17. The composite cured product according to claim 11, wherein the amorphous material is obtained by curing papermaking sludge as industrial waste. 18. The composite cured product according to claim 1, further comprising an inorganic powder. 19. The composite cured product according to claim 1, further comprising a binder. 20. A composite cured product according to any one of claims 1 to 9, or 11 to 17, wherein the fibrous material is oriented. 21. A composite building material in which a reinforcing layer is formed on at least one surface of a core material, wherein the composite hardened body according to claim 1 is applied to the core material. And composite building materials.