JP2000234298A - Composite cured product and composite building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite cured product which has excellent processability, excellent productivity and excellent flexural strength in a wet state and is suitable as a core material for building materials, by mixing an inorganic amorphous material with a fibrous substance having its length in a specific range. SOLUTION: A plate-like composite cured product 1 where a 3-10 mm long fibrous substance 3 is contained in an inorganic amorphous substance 2 in an amount of >=1 wt.%, preferably 2-75 wt.%, based on the total amount of the product is obtained by adding a mixture of the alkoxides or hydroxides of Al, Si, Ca, and the like to a sludge containing 3-10 mm long fibers for making paper such as toilet paper, subjecting the mixture to a hydrolysis reaction or the like in the presence of an alkali, drying and curing the reaction product to form a gel, carrying the gel with a conveyer, simultaneously pressing the carried gel with rolls to form a sheet, and then heating and compressing the sheet. A reinforcing sheet is laminated to at least one of the surfaces of the cured product 1 to form a composite building 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. In other words, in the construction industry, which has consumed a large amount of forest resources until now, by newly seeking construction materials 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.

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.

However, the technique disclosed in Japanese Patent Application Laid-Open No. 7-41350 has a problem that the workability is poor due to the use of iron plate and cement, and the productivity is reduced because the cement needs curing.

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] Further, any of the techniques uses cement, so that nails or the like cannot be hit, and if forcedly hit, there is a disadvantage that cracks are generated.

[0007]

SUMMARY OF THE INVENTION On the other hand, the inventors of the present invention have previously disclosed Japanese Patent Application No.
In the specification of Japanese Patent No. 1-222362, a proposal was made on a composite cured product containing an amorphous material composed of two or more oxides. This composite cured product has excellent bending strength and does not cause cracking due to hitting with a nail or the like, and therefore is particularly suitable for use as a building material.

The present inventors have further developed this technology,
A method for reducing the specific gravity and improving the strength was studied.

[0009] It is an object of the present invention to propose a composite cured body that is lighter and has improved strength, and a composite building material using the composite cured body.

[0010]

The gist of the present invention is as follows.
It is as follows. (1) A composite cured product, wherein a fibrous material having a length of 3 to 10 mm is mixed in an inorganic amorphous material in an amount of 1% by weight or more based on the total weight of the composite cured product.

(2) In the inorganic amorphous material, the length 3
The composite cured product according to (1), wherein a fibrous material containing a fibrous material of 10 to 10 mm is contained in an amount of 2 to 75% by weight based on the total weight of the composite cured product.

(3) 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 formed by using the composite cured body according to (1) or (2). And composite building materials.

In the composite cured product of the present invention, a fiber material having a relatively long fiber length of 3 to 10 mm is contained in an inorganic amorphous material in an amount of 1% by weight or more based on the total weight of the composite cured product. , Preferably in a proportion of 20% by weight or less. For this reason, a void can be formed between the fibers and the specific gravity can be reduced, and the strength can be improved because the fibrous material is complicatedly entangled with the inorganic amorphous material by the long fiber.

[0014]

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 includes an amorphous body 2 composed of two or more kinds of oxides and a water absorption preventing agent (including a water repellent) (not shown). Basically, objects 3 are mixed. Here, the amorphous body composed of a system of two or more oxides refers to the oxide (1)
-Oxide (2) ...-Oxide (n) (where n is a natural number, and oxide (1), oxide (2), ..., oxide (n) are different oxides ) Is an amorphous body.

Although it is difficult to accurately define such an amorphous substance, it is an amorphous compound which is formed by 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
and at least two types selected from n), and a halo is observed in the range of 2θ: 10 ° 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.

In this composite cured product 1, the amorphous material 2 becomes a strength-developing 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, metal and / or non-metal 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 composed of the Al ₂ O ₃ —SiO ₂ —CaO system includes 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 and SiO ₂
And CaO, it is considered to include any of the compounds formed by solid solution or hydration reaction or the like. In such an inorganic amorphous compound, Al, Si, and Ca are confirmed by fluorescent X-ray analysis, and a halo is observed in the range of 2θ: 10 ° to 40 ° in an analysis chart by X-ray diffraction.

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 the oxides is two or more, that is, Al
_{If it is a 2} O ₃ —SiO ₂ —CaO—oxide (n) -based (n is a natural number of 2 or more) amorphous material, these oxides, for example, oxide (1), oxide (2). ..Oxide (n)
(N is a natural number of 2 or more, and the oxide (n) means a different oxide if the value of n is different, and Al ₂
O ₃ , SiO ₂ and CaO), a compound formed by solid solution or hydration reaction with at least two kinds of combinations selected from the group consisting of
Compounds formed by performing a solid solution or hydration reaction with at least two combinations selected from ₂ O ₃ , SiO ₂ and CaO, and oxides (1), oxides (2),.
An oxide (n) (n is a natural number of 2 or more) and at least one selected from the group consisting of Al ₂ O ₃ and SiO <sub>2
2. It</sub> is considered to include any of the compounds formed by solid solution or hydration reaction in combination with at least one selected from CaO.

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 at least two types), and in the analysis chart by X-ray diffraction, 2θ: 10 ° to
Halos can be seen in the range of 40 °.

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 is roughened 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 amorphous body is 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 7.3 wt% SO relative to the total weight of _3: 0.1-3.5 wt% K ₂ O with respect to the total weight of the composite hardened product: 0 relative to the total weight of the composite hardened 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.

Incidentally, it can be confirmed by X-ray diffraction whether or not it has an amorphous structure. That is, 2θ: 10 ° 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 those having a completely amorphous structure, Hydrogen Aluminum Silicate, Kaolinite, Zeolit
e, Gehlenite, syn, Anorthite, Melitite, Gehlenit
e-synthetic, tobermorite, xonotlite, ettringite
Or SiO ₂ , Al ₂ O ₃ , CaO, Na ₂ O, Mg
O, P ₂ O ₅ , SO ₃ , K ₂ O, TiO ₂ , MnO, F
oxides such as e ₂ O ₃ and ZnO, and CaCO ₃
Crystals such as (Calcite) 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 Al ₂ O ₃ —SiO ₂ based crystalline compound is selected from the group consisting of Hydrogen Aluminum Silicate and 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.

Here, in the composite cured product of the present invention, halogen may be added to an amorphous material composed of at least two or more types of 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. Because, when the content is less than 0.1% by weight, the strength is low,
If the content 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.

The addition of a binder is also advantageous for further improving the strength, 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.

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 consisting of
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 desirably 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.

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 fibrous material has a length of 3
It is necessary to have at least 3% by weight of 10 mm to 10 mm. If the length is less than 3 mm, the entanglement for improving the strength is insufficient, and if the length is too long, the voids become too large, and in any case, the strength of the inorganic cured product is reduced. The content of the fibrous material is 3 to 10 m.
It is desirable that the content be 2 to 75% by weight including a fibrous material having a length of m. The reason for this is that if the content is less than 2% by weight, the strength of the composite cured product decreases, whereas if it exceeds 75% by weight, the fire protection performance and
This is because water resistance, dimensional stability, and the like may be reduced.

Further, in the composite cured product of the present invention, it is important to include a water absorption inhibitor (including a water repellent). That is, when a water absorption inhibitor (including a water repellent) is added to the composite cured product, the water absorption of the composite cured product is first suppressed, so that a decrease in strength due to water absorption can be avoided. In addition, by suppressing the amount of water absorption, it is possible to prevent cracking due to repeated freezing and melting of the water that has been absorbed.

In order to obtain these effects, it is preferable to add a water-absorbing inhibitor (including a water-repellent agent) in an amount of 0.1 wt% or more to the composite cured product. 0.1 ~ 10.0wt to reduce the strength of the body
%, More preferably in the range of 0.2 to 4.0 wt%.

Here, the water absorption preventing agent has a function and an effect of preventing water from entering the inside of the composite cured product.
Specifically, rosin, paraffin, silicone,
Fatty acid type, acrylic type and lecithin type, latex type, reactive sizing agent, stearic acid type, modified petroleum resin type, micro wax type, silane type, polyvinyl chloride,
Polyvinyl acetate, epoxy resin, urethane resin, styrene, methacrylic acid, starch, polyimide, polyester, phenolic resin, succinic acid, and the like can be used.

The water repellent may be uniformly added to the composite cured product or may be added only to the surface layer of the composite cured product. That is, a predetermined amount is mixed and added uniformly at the time of mixing the raw materials, and the water absorption preventing agent is dispersed and molded. A predetermined amount is applied to the surface of the composite cured product by a brush, a roll, a spray, or the like, and dried, heat-cured, cured, etc. to form a coating film.

It is recommended that the above-mentioned composite cured product is obtained by drying and coagulating and hardening industrial waste, and especially the one obtained by drying and coagulating and hardening papermaking sludge (scum). 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.

When mixing the raw materials, the water-absorbing inhibitor is added to the raw materials directly or diluted with water, a solvent, or the like, and added, followed by uniform mixing. After the composite is cured and molded, a predetermined amount is applied to the surface of the cured product using a brush, a roller, a spray, or the like, and a coating film or a thin layer is formed by drying, heat curing, or curing.

Further, in the papermaking sludge, in addition to 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.

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
More than species can be used. In particular, as industrial waste powder,
It is desirable to use at least one or more types of industrial waste powders selected from calcined powder of papermaking sludge, grinding dust of glass, and grinding dust of silica sand. Because, by using these industrial waste powder, cost reduction can be realized,
This is because it can further 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 or more inorganic substances 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 papermaking sludge containing fibers having a maximum length of 3 to 10 mm, papermaking sludge of toilet paper is desirable. This is because the maximum fiber length is long because waste paper is used.

The 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.

The addition or application of the water absorption preventing agent is as described above.

In particular, to mold the composite cured product into a plate,
The papermaking sludge is conveyed by a conveyor and pressed by a roll to form a sheet-like molded body. The sheet-like molded body is pressed while being heated at a heating temperature of 80 to 160 ° C. to form a plate-like 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 and hydroxides of Al, Si, Ca and a crushed material obtained by crushing waste paper are mixed, and the mixture is hydrolyzed and polymerized in the presence of an acid or alkali to form a sol. May be gelled. 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.

The composite building material is manufactured as follows. First, while transporting paper sludge on a conveyor,
Pressed with a roll to form a sheet-like molded body. 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 together while heating to form a composite building material including a core material (composite cured body) and a reinforcing layer. The heating temperature here is 80-200 ° C, and the pressure is 1-20k
About gf / cm ² is appropriate. Here, the term “pressing” refers to maintaining the pressure applied.

In place of the above-mentioned production method, a mat of inorganic fibers was impregnated with the resin composition, 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 a glass fiber, rock wool, or ceramic fiber is used as a 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.

[0067]

(Example 1) Unfired papermaking sludge discharged from a toilet paper manufacturing plant (having a solid content of 34% by weight and a water content of 66% by weight, having a maximum fiber length of 5 mm and a length of 3 to 5 mm) The fibers contained 5% by weight based on the total fiber weight, and the measurement was performed by filtering the papermaking sludge with a # 100 sieve and measuring the weight of the fibers remaining in the sieve. Length 3-5 for total weight
The weight of fibers in mm is about 2.5%. ) 1512 parts by weight were prepared. Then, paraffinic absorption inhibitor (solid content 50 parts by weight, water content 50 wt%) was added 4.1 parts by weight, sufficiently mixed, while conveying the homogeneous dispersion papermaking sludge conveyor, a pressure of 3 kgf / cm ² And 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 composite cured product thus obtained was analyzed using an X-ray fluorescence analyzer (RIX2100, manufactured by Rigaku), it was found that the composition had the following composition 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: 22.8 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% paraffinic: 0.3 wt%, other trace

(Example 2) After impregnating a phenolic resin solution obtained by adding a curing agent to a sheet-like glass fiber (impregnation amount: 45% in terms of solid content), the sheet-like glass fiber 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, the reinforcing sheet was placed on the front and back surfaces of the plate-shaped composite cured product of Example 1 and pressed at a temperature of 110 ° C. under a pressure of 7 kgf / cm ² for 20 minutes. A composite building material composed of 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.

Comparative Example 1 Unfired papermaking sludge discharged from a toilet paper manufacturing plant (solid content: 34% by weight, moisture: 66% by weight, maximum fiber length: 5 mm,
It contains 5% by weight of fibers having a length of 3 to 5 mm based on the total fiber weight. ) 1512 parts by weight were prepared and crushed with a ball mill for 5 hours to obtain a maximum fiber length of 2 mm. A plate-shaped composite cured product was obtained in the same manner as in Example 1 using this papermaking sludge.

Comparative Example 2 Unfired papermaking sludge discharged from a toilet paper manufacturing plant (solid content: 34% by weight, water content: 66% by weight, maximum fiber length: 5 mm,
It contains 5% by weight of fibers having a length of 3 to 5 mm based on the total fiber weight. ) 1512 parts by weight were prepared, to which was added water to waste paper and crushed with a ball mill for 1 hour (maximum fiber length: 12 mm). A plate-shaped composite cured product was obtained in the same manner as in Example 1 using this papermaking sludge.

The cured composites and composite building materials of the above examples and the composite cured product of the comparative example were subjected to bending strength, compressive strength, workability, nailing properties, and cracking properties during freezing and drying when absorbing moisture. Was tested. Table 1 shows the results. The test method was such that the bending strength was JIS A
In accordance with the method specified in 6901, and the compression strength
The measurement was performed according to the method specified in 5416, respectively. The bending strength at the time of moisture absorption is based on JIS A
After the composite cured product was absorbed in moisture according to the method specified in 1437, the bending strength was measured according to the method specified in JIS A 6901.

[0073]

[Table 1]

Further, with respect to the composite cured product of Example 1, X
The crystal structure was confirmed by line diffraction. The X-ray diffraction charts are shown in FIGS. 4 and 5, respectively. Note that the X-ray diffraction was performed by using Rigaku MiniFlex and targeting Cu. 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, calcium carbonate crystals (Ca
lsite), Kaolinite and SiO ₂ crystals were identified.
The content of calcium carbonate was 9.8% by weight based on the composite cured product in terms of a converted value.

[0075]

As described above, the composite cured product of the present invention is an inexpensive material that is excellent in workability and productivity and has high bending strength not only when dry but also when absorbing moisture. According to the present invention, it is possible to provide an optimum material for a building material exterior material at a low cost, since it can be advantageously applied in the field, and in particular, has excellent water resistance and can drive nails. be able to.

The composite building material of the present invention has excellent water resistance due to the characteristics of the above-mentioned composite cured product of the present invention,
According to the present invention, it is possible to provide an exterior material of a building material at a low cost because nails can be driven.

[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 an X-ray diffraction chart of the composite cured product of Example 1.

FIG. 5 is an X-ray diffraction chart of the composite cured product of Example 2.

[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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kenji Sato 1-1, Ibigawa-cho, Ibi-gun, Gifu Prefecture F-term in the Ogaki-Kita Plant (reference) 2E162 FA05 FA09 FA13 FA14 FA19 FA20 FB07 FC01 FD04 4F100 AA00A AA18 AA19 AA20 AA21 AA25 AH01H AK01B AK01C AK33 BA01 BA02 BA03 BA06 BA10B BA10C BA13 CA30 DG01A DG02 DG10 DH00B DH00C EJ17 EJ42 EJ82 GB07 HB00 JA12A JB07 JB13B JB13 J04A01 J02A04

Claims (3)

[Claims] 1. A composite cured product characterized in that a fibrous material having a length of 3 to 10 mm is mixed in an inorganic amorphous material in an amount of 1% by weight or more based on the total weight of the composite cured product. 2. The method according to claim 1, wherein said inorganic amorphous material has a length of 3 to 1
2. The composite cured product according to claim 1, wherein a fibrous material including a 0 mm fibrous material is contained in an amount of 2 to 75% by weight based on the total weight of the composite cured product. 3. 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 formed by using the composite cured body according to claim 1 or 2. Composite building materials.