JP3462185B2 - Cured body - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hardened body capable of mass-producing a hardened body having a plate-like solidified papermaking sludge, a method for producing the hardened body, and an apparatus for producing the hardened body.

[0002]

2. Description of the Related Art In recent years, effective utilization of various industrial wastes has been studied from the viewpoint of protecting the global environment. For example, in the building industry, which has consumed a large amount of forest resources up to now, by newly requesting industrial waste for building materials,
It has been proposed to reduce the consumption of forest resources. On the other hand, it has been required to realize cost reduction and high functionality of conventionally used inorganic boards such as calcium silicate board, perlite board, slag gypsum board, wood chip cement board and gypsum board.

The inventors of the present invention propose a technique for producing a cured product which can be effectively used as a building panel or the like by dewatering and pressing the papermaking sludge generated after the production of paper and then curing it. Proposed as -352586.

[0004]

The present inventor has shown in the above patent that a cured product can be obtained by curing the papermaking sludge, but it was not possible to produce a cured product in a profitable manner. . In order to actually mass-produce a cured product, first of all, it was necessary to establish a technique for gradually reducing the water content from the obtained paper product containing a large amount of water content.

Further, the papermaking sludge is colored due to the influence of ink and pulp impurities. In the dehydration press method, impurities remain as they are in the cured product, and the lightness of the cured product is reduced, resulting in coloring. There was a problem that it could not be decorated.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing a cured product and an apparatus for producing a cured product capable of efficiently mass-producing a cured product from papermaking sludge. To provide.

Another object is to provide a cured product having high brightness.

[0008]

In order to solve the above-mentioned problems, the hardened products according to claims 1 to 3 of the present invention are made by making papermaking sludge into paper and hardening it, and oxidizing each of Si, Al and Ca. A cured product containing an organic fibrous substance composed of a polysaccharide and calcium carbonate in an inorganic amorphous substance composed of a substance, wherein Ca, Al and Si in the cured product are CaO and Al, respectively. Converted to ₂ O ₃ and SiO ₂ , C
aO / SiO ₂ ratio 0.2 to 7.9, CaO / Al ₂
It is a cured product in which the ratio of O ₃ is adjusted from 0.2 to 12.5. The lightness of this cured product is N5 or more as a value based on the regulation of JIS Z 8721.

A preferred method for producing a cured product is to make a raw material solution containing papermaking sludge into a paper by using a rotary drum made of a mesh, attach the papermaking sludge to the surface of the rotary drum, and make the papermaking product. The paper is transferred to a porous conveyor belt having continuous pores, dehydrated from the paper product while being conveyed by the conveyor belt, and then cut into a predetermined size to cure the paper product to obtain a cured paper sludge. Since the paper product is dehydrated while being conveyed by the conveyor belt, the water content in the paper product can be efficiently reduced, and the cured product can be mass-produced.

Since a cured product is manufactured by making a paper using a reticulated rotating drum, impurities are removed from the mesh, so that the impurities can be reduced and the brightness can be increased. A hardened body containing calcium carbonate, wherein the amounts of Ca, Al, and Si in the hardened body are CaO, Al ₂ O ₃ , and SiO ₂ respectively, and CaO /
Since the SiO ₂ ratio is adjusted to 0.2 to 7.9 and the CaO / Al ₂ O ₃ ratio is adjusted to 0.2 to 12.5, Ca
The amount of ingredients is increased and the brightness is improved. Further, it is also high in strength and nailing performance. Therefore, the lightness of the cured product can be N5 or more as a value based on the regulation of JIS Z8721.

According to JIS Z 8721, the ideal lightness of black is set to 0, the ideal lightness of white is set to 10, and the perception of the brightness is equal between these black lightness and white lightness. Each color is divided into 10 parts so as to obtain a rate, and is displayed by symbols N0 to N10. The actual brightness measurement is N0
To the color chart corresponding to N10. In this case, the first decimal place is 0 or 5. The lightness of the cured product is J
Since the value based on the regulation of IS Z 8721 can be N5 or more, coloring and decoration can be performed.

It is desirable that the crystal habit of the calcium carbonate is at least one form selected from a spindle shape, a square shape, a thin table shape, a cube or a column shape. This is because it has high whiteness and has corners that prevent it from getting entangled in fibers and falling off, and can be incorporated into a cured product even in papermaking.

When the papermaking sludge cement is added, its content is preferably 30% by weight or less. This is because the lightness decreases as the content of papermaking sludge cement increases. Also, it is recognized that the addition of cement reduces the strength.

JP-A-55-12853 discloses a technique of wire-pressing papermaking sludge for dehydration and hot-pressing. However, according to the "Shizuoka Prefectural Paper Industry Testing Station Report" issued in 1979, the sludge at that time had only about 2.6% by weight in terms of CaO and the strength was not sufficient. In addition, since it is not a papermaking process, it contains a large amount of impurities and its brightness is low.

In Japanese Patent Publication No. 57-19019, a mixture of papermaking sludge and montmorillonite is press-molded. The papermaking sludge at that time contained a small amount of Ca and was not a Ca-based crystal, and was compressed. Inferior in strength etc. Japanese Patent Laid-Open No. 50-101604 discloses a board in which papermaking sludge and hydrophobic fibers are mixed and a binder is added. However, as a papermaking sludge at that time, it contained less Ca and had a bending strength of 2.5.
It is kg / cm ² , and even if it is compounded and has high strength,
Only about 15 kg / cm ² , the present invention is far superior. Japanese Unexamined Patent Publication No. 52-90585 discloses a papermaking sludge whose surface is treated with paraffin. However, the papermaking sludge at that time contained a small amount of Ca,
It is considered to be inferior in strength. In any case, since it is not a papermaking method, a large amount of impurities are contained, and the brightness is low after all.

Further, since a hardened material is manufactured by making a paper using a reticulated rotary drum, impurities are removed from the mesh, so that the impurities can be reduced and the brightness can be increased. Incidentally, in JP-A-49-114628, a mixture of 3% diluted papermaking sludge and cement is made into paper by a rotating drum, transferred from the drum surface onto a band blanket, dehydrated and pressed, and further wound roll. Disclosed is a technique in which the layer thickness is increased by the method described above and then the sheet is cut and conveyed. However, with this technique, the ratio of CaO is small, and the brightness decreases. Further, cement is contained in an amount of 55% or more, which also causes a decrease in brightness. Also,
Japanese Unexamined Patent Publication No. 59-156956 discloses a papermaking method using a round wire net, but the matting is made one by one to form a multi-layer, which is inefficient.

In a preferred method for producing a cured product, since the concentration of the raw material solution containing the papermaking sludge is 0.5 to 25% by weight of solid content, the papermaking sludge is improved in papermaking property and the cured product is efficiently prepared. Can be mass-produced. That is, the concentration is 0.
This is because if it is less than 5%, it is not possible to efficiently perform papermaking from the raw material solution using the rotary drum made of a mesh, and if it exceeds 25%, the uniformity of the product is deteriorated.

In a preferred method for producing a hardened product, the paper product on the conveyor belt is transferred to a cutting rotary drum to form multiple layers, and the multi-layered product product is cut when a predetermined thickness is reached. Therefore, it is possible to continuously form a paper product having a uniform thickness.

In a preferred method for producing a cured product, the cut paper product is further multilayered and then pressed under pressure. Therefore, a cured product having a required thickness can be easily manufactured.

In a preferred method for producing a cured product, pressure pressing is performed at 10 to 250 Kg / cm ² . Press the press at 10Kg / cm ²
If it is less than the required strength, the required strength cannot be obtained. On the other hand, the strength cannot be increased even when pressure-pressed at a pressure exceeding 250 kg / cm ² , and the press device becomes large and expensive. Also, while transporting with a transport belt,
Since it is possible to remove impurities and ink when dehydrating, it is optimal for increasing the brightness.

A preferred apparatus for producing a hardened body comprises a rotary drum formed of a net-like body for making a raw material solution containing papermaking sludge and attaching the papermaking sludge papermaking body to the surface, and the papermaking body attached to the surface of the rotary drum. Porous carrier belt that transfers and dehydrates while transporting, cutting device that cuts the paper product conveyed by the conveyor belt to a predetermined size, and curing of the cut paper product to cure papermaking sludge And a curing device for obtaining a body. Since the paper product is dehydrated while being conveyed by the conveyor belt, the water content in the paper product can be efficiently reduced, and the cured product can be mass-produced. Further, since the rotary drum made of a mesh is used, the papermaking product can be continuously made from the raw material solution, and the hardened product can be efficiently mass-produced from the papermaking sludge. Further, since a cured product is manufactured by making a paper using a reticulated rotary drum, impurities are removed from the mesh, so that the impurities can be reduced and the brightness can be increased.

In the preferred apparatus for producing a hardened body, since the rotating speed of the rotating drum is 1 to 100 times / minute, a papermaking body can be produced from a raw material solution with high efficiency, and a hardened body can be efficiently mass-produced from papermaking sludge. It becomes possible to do. Here, if the rotating drum is lower than 1 rotation / minute, the papermaking efficiency is low. on the other hand,
When the rotation speed exceeds 100 rotations / minute, it becomes difficult to form a paper product with a uniform thickness.

In a preferred apparatus for producing a cured product, a plurality of rotary drums are provided along the conveyor belt, and the paper product is transferred while being multi-layered on the conveyor belt. Therefore, it is possible to produce a paper product with high efficiency from the raw material solution and efficiently produce a hardened product from the papermaking sludge.

In a preferred apparatus for producing a cured product, the rotary drum has a mesh structure of # 40 to 150. Therefore, it is possible to efficiently make a paper product from the raw material solution and efficiently mass-produce a hardened product having a high density from the papermaking sludge.
Here, if the mesh is rougher than that of # 40, only the inorganic non-crystalline material will escape from the raw material solution, and the density and strength of the cured material will decrease. On the other hand, if the mesh is finer than that of # 150, the moisture will not escape so well that it will not be possible to make a paper product from the raw material solution with high efficiency.

In the preferred apparatus for producing a cured product, since the transport speed of the transport belt is 5 to 80 m / min, it is possible to efficiently produce a paper product having a proper thickness from the raw material solution and efficiently from the papermaking sludge. It becomes possible to mass-produce the cured body. Here, if the conveying speed is lower than 5 m / min, the papermaking product can be made thicker, but the papermaking efficiency is low. On the other hand, the transport speed is 80
When it exceeds m / min, the paper product becomes thin and it is difficult to obtain a uniform thickness, and the paper product may be broken.

A preferable apparatus for producing a hardened body comprises a cutting rotary drum in which the cutting apparatus makes multiple layers while transferring the paper-making body. Then, when the multi-layered paper product on the surface of the rotary drum for cutting reaches a predetermined thickness, the extrusion mechanism is operated,
The paper product is cut at a position corresponding to the groove. Therefore, a paper product having a uniform thickness can be efficiently generated.

A preferred hardened body manufacturing apparatus is a cutting apparatus,
A blade for cutting the paper product whose one end is cut by the cutting rotary drum at regular intervals is provided. Therefore, it is possible to efficiently form a paper product having a predetermined length.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Here, first, the structure of a composite cured product produced by a method for producing a composite cured product of the present invention described later will be described with reference to the schematic view of FIG. The composite cured body 1 is an inorganic amorphous body 2 composed of a system of two or more kinds of oxides.
And the organic fibrous material 3 is mixed in the inorganic amorphous material 2. The inorganic amorphous body composed of a system of two or more kinds of oxides as used herein means an oxide (1) -oxide (2) ...- Oxide (n) system (where n is a natural number, Oxide (1), Oxide (2), ... Oxide (n)
Are amorphous bodies of different oxides).

It is difficult to accurately define such an amorphous substance, but it is an amorphous compound which is produced by solid solution or hydration reaction of two or more kinds of oxides. Conceivable. Such an inorganic amorphous compound is obtained by fluorescent X-ray analysis, and the elements (Al, Si,
Ca, Na, Mg, P, S, K, Ti, Mn, Fe, Z
(At least two or more selected from n) are confirmed, and a halo is seen in the range of 2θ: 10 ° to 40 ° in the chart of analysis by X-ray diffraction. This halo is a gentle undulation of X-ray intensity and is observed as a broad bulge on the X-ray chart. The halo has a half width of 2θ:
It is 2 ° or more.

The above-mentioned composite cured body 1 is first prepared as an inorganic amorphous body 2.
Serves as a strength-developing substance, and since the organic fibrous material 3 is dispersed in the inorganic amorphous material 2 to improve the fracture toughness value, the bending strength value and the impact resistance can be improved. Also,
A homogeneous cured product having no anisotropy in strength can be obtained. Further, since it is an amorphous material, it has an advantage that sufficient strength can be obtained at a low density.

The reason why the above-mentioned amorphous body becomes a strength-developing substance is not clear, but it is presumed that it is because the progress of cracks is hindered as compared with the crystalline structure. Further, it is considered that the fracture toughness value is improved because the fibrous material is more likely to be uniformly dispersed in the amorphous material than in the crystalline material. As a result, even if a nail is driven in or a through hole is provided,
Since it does not cause cracks, it is most suitable for construction materials and other materials that require processing.

Here, as the oxide, a metal and / or non-metal oxide can be used, and Al ₂ O ₃ and Si can be used.
O ₂ , CaO, Na ₂ O, MgO, P ₂ O ₅ , SO ₃ ,
It is desirable to be selected from K ₂ O, TiO ₂ , MnO, Fe ₂ O ₃ and ZnO. In particular, Al ₂ O ₃ -S
iO ₂ -CaO-based or Al ₂ O ₃ -SiO ₂ -CaO
-Amorphous materials composed of oxides or composites of these amorphous materials are most suitable. The oxide in the latter amorphous body is one or more kinds of metal and / or nonmetal oxides other than Al ₂ O ₃ , SiO ₂ and CaO.

First, the amorphous body composed of Al ₂ O ₃ --SiO ₂ --CaO system is composed 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 of (2) 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 are considered to include any of the compounds formed by solid solution or hydration reaction.

Such an inorganic amorphous compound has fluorescence X
By line analysis, Al, Si, and Ca are confirmed, and the halo is observed in the range of 2θ: 10 ° to 40 ° in the chart of the analysis by X-ray diffraction.

Also, Al ₂ O ₃ , SiO ₂ and CaO
Other than that, a system containing at least one oxide, that is, Al
Non Akirashitsutai consisting ₂ O ₃ -SiO ₂ -CaO- oxide, in addition to the combination of the above Al ₂ O ₃ -SiO ₂ -CaO-based, oxide and Al ₂ O _3, SiO ₂ and oxides , C
aO and oxide, Al ₂ O ₃ and SiO ₂ and oxide, SiO
₂ and CaO and oxides, Al ₂ O ₃ and CaO and oxides, and Al ₂ O ₃ and SiO ₂ and CaO and oxides. It is considered to include.

It should be noted that the number of oxides is 2 or more, that is, Al
₂ O ₃ —SiO ₂ —CaO—oxide (n) type (n is a natural number of 2 or more) amorphous substance, these oxides, for example, oxide (1), oxide (2). ..Oxide (n)
(N is a natural number of 2 or more, and oxide (n) means different oxides if the value of n is different, and
₂ O ₃ , SiO ₂ , and CaO are excluded), a compound formed by solid solution or hydration reaction with a combination of at least two selected from Al ₂
Compounds formed by solid solution or hydration reaction with a combination of at least two kinds selected from O ₃ , SiO ₂ , and CaO, and further oxide (1), oxide (2) ...
At least one selected from each of oxides (n) (n is a natural number of 2 or more), Al ₂ O ₃ , SiO ₂ , and Ca.
It is considered to include any of the compounds formed by solid solution or hydration reaction in combination with at least one selected from O.

Such an inorganic amorphous compound has fluorescence X
By line analysis, in addition to Al, Si, and Ca, the elements (Na, Mg, P, S, K, Ti, Mn, F) that constitute the oxide
e, at least two or more selected from Zn) are confirmed, and 2θ: 10 ° ~ in the chart of analysis by X-ray diffraction.
The above halo can be seen in the range of 40 °.

Here, Al ₂ O ₃ , SiO ₂ and Ca
The oxide to be combined with O is at least one kind, and is a metal excluding Al ₂ O ₃ , SiO ₂ , and CaO and / or
Or a non-metal oxide can be used, eg 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 properties expected of the composite cured product.

For example, Na ₂ O or K ₂ O can be removed with an alkali or the like. Therefore, if the removal treatment is performed prior to the plating treatment, the surface of the composite cured body to be plated becomes rough and it acts as an anchor for plating. be able to. Mg
O contributes to strength development by forming a solid solution with Al ₂ O ₃ , SiO ₂ and CaO, and greatly improves bending strength and impact resistance. P
₂ O ₅ is particularly advantageous when it is used for a biomaterial (artificial root, artificial bone) because it assists adhesion with bone. SO ₃
Has a bactericidal action and is suitable as an antibacterial building material. TiO
₂ is a white coloring material and also acts as a photo-oxidation catalyst, so it can forcibly oxidize the attached organic pollutants and can be cleaned simply by irradiating light with building materials or various filters. It 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 may exist individually in the amorphous material.

The composition of the above-mentioned amorphous material is Al ₂
Converted to O ₃ , SiO ₂ and CaO, Al ₂ O ₃ :
3 to 51% by weight, based on the total weight of the cured composite, Si
O ₂ : 6 to 53% by weight with respect to the total weight of the composite cured product, and CaO: 6 to 63% by weight, preferably 8 to 63% by weight, with respect to the total weight of the composite cured product, and their sum is 1
It is preferably contained in a range not exceeding 00% by weight.

Because the content of Al ₂ O ₃ is 3% by weight
If the content is less than 51% by weight or less than 51% by weight, the strength of the composite cured product decreases, and if the SiO ₂ content is less than 6% by weight or more than 53% by weight, the strength of the composite cured product decreases. Further, the content of CaO is less than 8% by weight or 63
Even if it exceeds the weight percentage, the strength of the composite cured product is lowered.

Further, converted to oxide, CaO / SiO
_It is advantageous to adjust 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 to obtain a cured product having high strength.

The CaO / SiO ₂ ratio is optimally more than 0.2 and 7.9 or less, and the CaO / Al ₂ O ₃ ratio is optimally more than 0.2 and 12.5 or less. In addition, these, Ca, A
l, amount of Si (CaO, Al ₂ O ₃ , SiO ₂ equivalent)
Is the total amount of Ca, Al, and Si in the composite hardened body, and for example, in the case of Ca, is the total amount of Ca in the calcium carbonate and the inorganic amorphous body.

Al ₂ O ₃ , SiO ₂ and CaO
Other oxides such as 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 type or two or more types are contained among nO, the suitable content of each component is as follows. Needless to say, the total amount of these oxides does not exceed 100% by weight. Na ₂ O: 0.1-1. To the total weight of the cured composite.
2 wt% MgO: 0.3 to 1 with respect to the total weight of the cured composite
1.0 wt% P ₂ O ₅ : 0.1 to 7 with respect to the total weight of the cured composite.
3% by weight SO ₃ : 0.1 to 3 based on the total weight of the composite cured product.
5% by weight K ₂ O: 0.1 to 1. based on the total weight of the composite cured product.
2% by weight TiO ₂ : 0.1 to 8 with respect to the total weight of the cured composite.
7 wt% MnO: 0.1-1.
5 wt% Fe ₂ O _3: 0.2~1 on the total weight of the composite cured body
7.8 wt% ZnO: 0.1-1.
8 wt% The reason for limiting the content of these oxides to the above range is that the strength of the composite cured product decreases if the content is out of the above range.

Whether or not it has an amorphous structure can be confirmed by X-ray diffraction. That is, 2θ: 10 ° by X-ray diffraction
If a halo is observed in the region of -40 °, it can be confirmed that the halo has an amorphous structure. In addition, in the present invention, in addition to those having a completely amorphous structure, Hydrogen Aluminium Silicate, Kaolinite, and Zeolit are included in the amorphous structure.
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 these crystals are not considered to be strength-developing substances themselves, for example, they are effective in improving the compressive strength by increasing hardness and density and suppressing the development of cracks. Conceivable. The content of the crystal body is preferably 0.1 to 50% by weight with respect to the total weight of the composite cured body. This is because when the content of the crystal is less than 0.1% by weight, the effects such as increasing hardness and density to improve the compressive strength and suppressing the development of cracks cannot be sufficiently obtained. This is because the bending strength is lowered.

By the way, the above-mentioned Al ₂ O ₃ —SiO ₂ -based crystalline compound is Hydrogen Aluminum Silicate, Kaolini.
te, Zeolite, Al ₂ O ₃ —CaO crystalline compound is Calcium Aluminate, CaO—SiO ₂ crystalline compound is Calcium Silicate, Al ₂ O ₃ —SiO ₂ —Ca
The O-based crystalline compounds are Gehlenite, syn and Anorthite, and the Al ₂ O ₃ —SiO ₂ —CaO—MgO-based crystalline compounds are Melitite and Gehlenite-synthetic.
Further, it is desirable that the above crystalline substance contains Ca, such as Gehlenite, syn (Ca ₂ Al ₂ O ₇ ), and Melitite-s.
_{ynthetic (Ca 2 (Mg 0.5 Al} 0.5) (Si 1. 5 Al
_0.5 O ₇ )), Gehlenite-synthetic (Ca ₂ (Mg
_0.25 Al _0.75 ) (Si _1.25 Al _0.75 O ₇ )), Anorthit
It may contain e, ordered (Ca ₂ Al ₂ Si ₂ O ₈ ) and calcium carbonate (Calcite).

Further, in the composite cured product produced by the production method of the present invention, halogen may be added to an amorphous body composed of a system of at least two kinds of oxides. This halogen acts as a catalyst for the reaction of producing a solid solution and a hydrate, and also acts as a combustion suppressing substance. Its content is 0.1-1.
2% by weight is desirable. 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. Although calcium carbonate itself is not a strength-developing substance, it is considered that the surrounding of calcium carbonate by an amorphous material contributes to the improvement of strength by the action of preventing the development of cracks. The content of this calcium carbonate is 48 with respect to the total weight of the cured composite.
It is preferably less than or equal to wt%. The reason for this is that if it exceeds 48% by weight, the bending strength will decrease. Moreover, 0.1% by weight or more is desirable. This is because if it is less than 0.1% by weight, the strength is not improved.

Further, the addition of a binder is also advantageous for further improving the strength, water resistance, chemical resistance and fire resistance. It is desirable that the binder is made of one or both of a thermosetting resin and an inorganic binder. As thermosetting resin, phenol resin,
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, as the organic fibrous material mixed in the inorganic amorphous material in the method for producing a composite cured product of the present invention, an organic fibrous material composed of a polysaccharide is used. Because there is an OH group in the polysaccharide, Al ₂ O ₃ by hydrogen bond,
This is because it is easy to bond with various compounds of SiO ₂ or CaO.

The polysaccharide is preferably at least one compound selected from amino sugar, uronic acid, starch, glycogen, inulin, lichenin, cellulose, chitin, chitosan, hemicellulose and pectin. As the organic fibrous material composed of these polysaccharides, generally, pulp, pulp dregs, and pulverized materials of waste paper such as newspapers and magazines are advantageously used.

The content of the fibrous material is 2 to 75.
It is desirable that the content is wt%. The reason for this is that if the amount is less than 2% by weight, the strength of the composite cured product will decrease, while if it exceeds 75% by weight, the fireproof performance, water resistance, dimensional stability, etc. may deteriorate. Furthermore, the average length of the fibrous material is preferably 10 to 1000 μm. This is because if the average length is too short, entanglement does not occur, and if it is too long, voids occur and the strength of the composite cured product tends to decrease.

The composite hardened body 1 described above is most preferably obtained by drying paper sludge (scum) and coagulating and hardening it. That is, the papermaking sludge is a pulp residue containing an inorganic substance, contains an organic fibrous substance, and uses industrial waste as a raw material, so that the cost is low and contributes to the solution of environmental problems. Moreover, this papermaking sludge itself has a function as a binder, and by itself or by kneading with other industrial waste,
It has the advantage that it can be molded into a desired shape.

In addition to pulp, Al ₂ O ₃ , SiO ₂ , CaO, Na ₂ O and Mg are contained in the papermaking sludge.
O, P ₂ O ₅ , SO ₃ , K ₂ O, TiO ₂ , MnO, F
It is common to contain crystals of e ₂ O ₃ and ZnO or a sol which is a precursor of these oxides, or a composite thereof, at least one selected from halogen and calcium carbonate, and water.

Here, as shown in FIG.
Mixing the inorganic particles 4 therein is advantageous for improving fire resistance and for reacting with an amorphous material to form a strength-developing substance to improve strength. By doing so, the specific gravity of the composite cured product can be adjusted.

As the inorganic particles 4, at least one selected from calcium carbonate, calcium hydroxide, shirasu, shirasu balloon, pearlite, aluminum hydroxide, silica, alumina, talc, calcium carbonate and industrial waste powder is used. it can. In particular, as the industrial waste powder, it is desirable to use at least one kind of industrial waste powder selected from a calcined powder of papermaking sludge, a polishing dust of glass, and a crushed dust of silica sand. This is because the use of these industrial waste powders makes it possible to realize cost reduction and contribute to solving environmental problems.

The inorganic particles obtained by firing the papermaking sludge can be obtained by heating the papermaking sludge at 300 to 1500 ° C. The inorganic particles thus obtained are
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 300 ℃ or more and 800 ℃
Inorganic particles obtained by firing at a temperature of less than 100 ° C. or by heat treatment at 300 to 1500 ° C. and then rapidly cooling are advantageous because they certainly contain an amorphous material. The inorganic particles 4 preferably have 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 particles will be small and the strength will be reduced.
If it exceeds m ² / g, the effects of crack development and hardness improvement are reduced, resulting in a reduction in strength.

Further, the inorganic particles 4 may contain at least one inorganic substance selected from silica, alumina, iron oxide, calcium oxide, magnesium oxide, potassium oxide, sodium oxide and phosphorus pentoxide. desirable. This is because 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 particles 4 is too small or too large, sufficient strength cannot be obtained.
It is desirable to be in the range of up to 100 μm. The content of the inorganic particles is preferably 10 to 90% by weight. That is, when the amount of the inorganic particles is too large, the strength decreases, and conversely, when the amount of the inorganic particles is too large, the strength becomes brittle, and in any case, the strength decreases.

Composite cured product 1 produced by the method of the present invention
Is used in various industries, calcium silicate plate,
It can be used for electronic materials such as new construction materials replacing perlite board, plywood, gypsum board, medical materials for artificial limbs, artificial bones, artificial tooth roots, core boards of printed wiring boards, interlayer resin insulation layers, etc. it can.

Next, embodiments of the method for producing a cured product and the apparatus for producing a cured product according to the present invention will be described with reference to FIGS. 3 to 9. In the production method of the present invention, the papermaking sludge is used as a raw material for the composite cured product without kneading with other industrial waste. The papermaking sludge used in the manufacturing method of the present invention includes printing / information paper, kraft paper, titanium paper,
Papermaking sludge discharged from pulp manufacturing process, raw material processing process such as waste paper, papermaking process when manufacturing tissue paper, dust paper, toilet paper, sanitary goods, towel paper, industrial hybrid paper or household hybrid paper, etc. desirable. Maruto Kiln Co., Ltd. handles papermaking sludge.

FIG. 3 shows the overall structure of the apparatus for producing a cured product. The apparatus for producing a cured product includes a raw material adjusting mechanism 10 for adjusting papermaking sludge to generate a slurry 14, a papermaking mechanism 20 for making a papermaking product 26 from the slurry 14, and a reversing device 40 for inverting the papermaking product 26. A press machine 50 that stacks the paper products 26 and then pressurizes and dehydrates the paper products, and a dryer 60 that forms the cured product 1 by drying the pressed paper products.
Consists of.

First, the raw material adjusting mechanism 10 for adjusting the raw material
This will be described with reference to FIG. Raw material 1
1 and water 12 were weighed so that the solid content would be 0.5 to 25% by weight by suction dehydration described later, and the mixer 13
A flocculating agent (flocking agent: an addition amount of 0.01 to 0.01) contained in aluminum sulfate, ferric chloride, polyaluminum chloride, sodium polyacrylate, polymethacrylic acid ester, polyacrylic acid ester, or polyacrylamide. 5%) and organic fibers such as vinylon fibers (binder: the addition amount is 0.1 to 10% by weight), and a mixer 1
Mix at 3 to prepare slurry 14. Organic fibers (binders) are synthetic fibers such as polyethylene, polypropylene and vinylon, pipes, pulp recovered from waste paper,
In addition, fibrous industrial waste can be used. As a raw material, various inorganic powders and resins can be further added to the papermaking sludge.

This slurry 14 is put on the bottom of the filter 1
6 is used to perform suction dehydration.
The concentration is adjusted to 0.5 to 25% by weight of solid content by suction dehydration. In the suction dehydration, the fibers of the papermaking sludge are not oriented, so that the obtained composite cured product is less likely to warp or crack.

A vacuum pump 17 is provided at the bottom of the dehydration container 15.
The vacuum pump 17 operates to draw in water. The filter 16 is not particularly limited, but includes a sintered metal, a porous metal plate (a metal plate with a hole having a diameter of 1 to 5 mm),
A porous ceramic filter, a porous resin, a glass fiber board, etc. can be used. The raw material 14 whose water content has been adjusted in the dehydration container 15 is temporarily stored in the chest tank 18.
The chest tank 18 is equipped with a propeller for stirring so that the solid content in the raw material does not settle.

In this embodiment, the water content is adjusted by the dehydration container 15. However, as shown in FIG. 4 (B), the dehydration container 15 is not used and only the amount of water added to the mixer 13 is adjusted. It is also possible to adjust the water content with.

Subsequently, the papermaking body 2 is made by the papermaking mechanism 20 from the slurry 14 containing the papermaking sludge whose water content has been adjusted as described above.
6 is generated. An inorganic binder such as cement or an organic binder such as resin may be added to the slurry (raw material solution). The papermaking mechanism 20 will be described with reference to FIG. The papermaking mechanism 20 includes three bats 21A, 21B, and 21C that store the slurry 14, and a wire cylinder 2 that is provided in the bat and that makes the slurry 14 into paper.
2A, 22B, 22C and wire cylinders 22A, 2
2B and 22C, a conveyor belt 23 that transfers and conveys the papermaking body 26, a rotary drum 30 for cutting that winds and cuts the papermaking body 26 conveyed by the conveyance belt 23 to a predetermined thickness, and papermaking Cutter 36 for cutting body 26
And a belt conveyor 38 that conveys the papermaking body 26.

Wire cylinders 22A, 22B, 22C
Has a diameter of 70 cm and a width of 1 mm. In this embodiment, since the water body for performing the drainage (papermaking) is composed of the rotating drum (wire cylinder) composed of the mesh body, the papermaking body 26 can be continuously produced from the raw material solution 14, and the papermaking sludge can be efficiently used. It is possible to mass-produce cured products.
The water that has passed through the wire cylinders 22A, 22B, and 22C passes through the pipe 17a and the vacuum pump 17 as shown in FIG.
It is returned to the mixer 13 shown in (A).

Further, in this embodiment, the wire cylinder 2
Three papermaking machines 2A, 22B, 22C are provided along the conveyor belt 23, and the conveyor belt 23 is made to have a multi-layer structure.
6 is transferred. Therefore, from the raw material solution 14 to the papermaking body 26
Paper can be produced with high efficiency, and a cured product can be efficiently mass-produced from paper sludge. In this embodiment, the wire cylinder rotation speed is set to 60 rotations / minute. The number of rotations is preferably 1 to 100 times / minute. This is because the papermaking product 26 can be produced from the raw material solution 14 with high efficiency, and the hardened product can be efficiently mass-produced from the papermaking sludge. Here, if the rotating drum is lower than 1 rotation / minute, the papermaking efficiency is low. On the other hand, when the rotation speed exceeds 100 rotations / minute, it becomes difficult to form a paper product with a uniform thickness. In this embodiment, three wire cylinders 22A, 22B, 22C are provided side by side, but one or more wire cylinders can be used.

The wire cylinders 22A, 22B,
22C mesh # 60 (60 meshes per inch)
Is formed in. Wire cylinders 22A, 22B,
The mesh of 22C is preferably # 40 to 150. The papermaking body 26 can be made into paper with high efficiency from the raw material solution (slurry) 14,
This is because it becomes possible to efficiently mass-produce a hardened body having a high density from the papermaking sludge. Here, if the mesh is rougher than that of # 40, only the inorganic non-crystalline material will escape from the raw material solution, and the density and strength of the cured material will decrease. On the other hand, if the mesh is finer than that of # 150, the moisture will not escape so well that it will not be possible to make a paper product from the raw material solution with high efficiency. Since flocs are formed in the papermaking sludge (raw material solution) by the aggregating agent, efficient papermaking can be performed.

The concentration of the raw material solution containing papermaking sludge is preferably 3.5 to 25% by weight of solid content. This is because it is possible to improve the paper-making property from the paper-making sludge and efficiently mass-produce the cured body. That is, if the concentration is less than 3.5%, it is not possible to efficiently perform papermaking from the raw material solution using the wire cylinder (draft body), and if it exceeds 25%, the uniformity of the product deteriorates.

Wire cylinders 22A, 22B, 22C
Conveyor belt 2 that transfers and conveys the paper made by papermaking
3 is made of felt having a width of 1 m and is suspended by rollers 34. A suction box 24 is provided on the back surface and dehydration is performed while suctioning with a vacuum pump 17. That is, the belt 23 adsorbs the moisture of the raw material 14 including the papermaking sludge into the pores of the felt, and the adsorbed moisture absorbs the moisture in the suction box 2.
4 and is adsorbed to the vacuum pump 17 side and returned to the mixer 13 shown in FIG. In the first embodiment, the belt 23 is made of felt, but instead of this, a porous resin having continuous pores, a porous rubber, inorganic fibers hardened with a binder or the like, sintered metal, A porous metal, a belt obtained by hardening a block of porous metal with a flexible binder such as rubber, or the like can be used. In this embodiment, the conveyor belt 23 is made of a porous material having continuous pores and dehydrates while being conveyed by the conveyor belt 23, so that the water content in the papermaking product 26 can be efficiently reduced.

Further, in this embodiment, the conveying speed of the conveying belt 23 is set to 48 m / min, and the wire cylinders 22A, 22B and 22C, the cutting rotary drum 30 and the belt conveyor 38 are synchronized with this. Are driven by a motor (not shown). The transport speed of the transport belt 23 is preferably 5 to 80 m / min. This is because it is possible to highly efficiently produce a paper product having an appropriate thickness from the raw material solution, and to efficiently mass-produce a cured product. Here, if the conveying speed is lower than 5 m / min, the papermaking product can be made thicker, but the papermaking efficiency is low. On the other hand, the transport speed is 80
When it exceeds m / min, the paper product becomes thin and it is difficult to obtain a uniform thickness, and the paper product may be broken.

The cutting rotary drum 30 for winding and cutting the paper product conveyed by the conveyor belt 23 to a predetermined thickness,
It has a diameter of 64 cm (outer circumference 2 m) and is provided with a storage groove 32 for retaining water on the surface and a piano wire 31 housed in a housing groove 33 located in the vicinity of the groove 32. The cutting rotary drum 30 is wound around the surface of the papermaking product 26 conveyed from the conveyor belt 23 in a multilayer structure.

Then, the papermaking product 26 has a predetermined thickness (1.5
cm), which is detected by a sensor not shown,
The piano wire 31 in the housing groove 33 is pushed out. Storage groove 3
2 has a high water content, and when the piano wire 31 is pushed out, the papermaking product 26 is cut along the storage groove 32, and the cut end has the cutting end on the side of the belt conveyor 38, as shown in FIG. 6 (A). Fall on. Then, with the rotation of the cutting rotary drum 30 and the conveyance of the belt conveyor 38, the papermaking product 26 having a predetermined thickness is conveyed onto the belt conveyor 38 (see FIG. 6B). Here, as shown in FIG. 6C, when the other cut end is conveyed to the corresponding position of the cutter 36, the cutter 36 is lowered to the belt conveyor 38 side,
The cut end of the papermaking product 26 and the unlaminated papermaking product carried on the carrying belt 23 are separated.

In this embodiment, the papermaking product on the conveyor belt 23 is transferred to the cutting rotary drum 30 to form a multilayer structure,
When the multi-layered paper product 26 reaches a predetermined thickness, it is cut into a predetermined size. By the rotary drum for cutting, the papermaking product 26 of uniform thickness (1.5 cm) and size (1 m x 2 m)
Since the resin can be continuously molded, it becomes possible to efficiently mass-produce the cured body.

Further, in this embodiment, the cutting rotary drum 3 is used.
A cutter 36 is provided for cutting the paper product 26, one end of which is cut at 0, at regular intervals. Therefore, the specified length (2
The papermaking product 26 of m) can be formed. Although the thickness of the papermaking product 26 is set to 1.5 cm in this embodiment, the thickness is preferably 2 cm or less. If the thickness is 2 cm or less, papermaking is easy, and handling is easy in transportation.

The reversing device 40 for reversing the paper product will be described with reference to FIG. In the manufacturing apparatus of this embodiment, since the paper products are laminated while being alternately inverted as will be described later, the paper products 26 are inverted every other sheet. The reversing device 40 includes a conveying device 42 that adsorbs and conveys a paper product, a table 44, and a reversing plate 46.

As shown in FIG. 7A, the papermaking product 26 on the belt conveyor 38 is transferred to the reversing plate 4 by the carrying device 42.
6 is placed. The reversal plate 46 is driven, and the papermaking body 46
Are reversed (see FIG. 7B). And FIG. 7 (C)
The papermaking product 26 inverted as shown in FIG. 3 is conveyed by the conveying device 42 to the pressing machine 50 shown in FIG. In addition,
As described above, in the present embodiment, the papermaking product 26 is made flexible by adding the binder to the slurry 14 to facilitate the handling after cutting.

Press machine 50 for dewatering by pressurizing the paper product.
Will be described with reference to FIGS. 8 and 9. Figure 8
As shown in (A), the press machine 50 includes a female die 54 having a recess 54A and a male die 52 fitted into the recess 54A.
The female mold 54 and the male mold 52 are respectively formed with minute through holes 54a and 52a for leading out water generated when the paper product is pressed. Further, the press machine 50 is provided with a curtain coater 56 for applying the raw material solution 14 to the papermaking body 26 (FIG. 8).
(See (B)).

Lamination and pressurization by the press machine 50 will be described. First, as shown in FIG. 8 (A), in the concave portion 54A of the female die 54, the lowermost layer is inverted by the reversing device 40 described above with reference to FIG. The papermaking body 26 whose contact surface side is directed downward,
It is carried in by the carrier device 42. Next, as shown in FIG. 8B, the raw material solution 14 is applied by the curtain coater 56 to the upper surface of the paper product 26, that is, the adhesive surface to the upper paper product. The amount of this raw material solution is
50g / m ² ~500g / m ² are preferred in solids. Although the curtain coater 56 is used here,
Various coating devices such as a roll coater can be used.

As the second-layer papermaking product, as shown in FIG. 8C, the papermaking product 26 on the belt conveyor 38 is carried into the recess 54A of the female die 54 by the carrying device 42 without being inverted. After that, as shown in FIG. 9A, after the raw material solution 14 is applied, the inverted papermaking product 26 of the third layer is applied.
Is placed, and after applying the raw material solution 14, the fourth layer (uppermost layer) of the non-inverted papermaking product 26 is placed and the stacking is completed. Here, four layers are laminated, but any number of sheets may be used as long as it is two or more, and when manufacturing a thin cured body, one sheet is also possible.

After that, the male die 52 is pushed down, and a pressure press is performed at 60 kg / cm ² (see FIG. 9 (B)). At this time, the water oozing out from the papermaking body 26 is led out to the outside through the through holes 54a and 52a. Then, the male die 52 is raised (see FIG. 9C), the composite cured body 1 formed by pressurization is taken out from the female die, and is conveyed to the dryer 60.

In this embodiment, pressure is applied to the mold (concave portion 54A).
Since it is carried out in the medium, the papermaking body 26 will not be torn even if it is pressurized at a high pressure, and it becomes possible to manufacture the high-strength cured body 1 from the papermaking sludge at a high yield. Further, since the male die 52 and the female side 54 are provided with through holes 52a and 54a for draining water that oozes out from the papermaking body 26, dehydration is performed at the time of pressurization, and the curing process by subsequent drying is completed in a short time. Can be done. Further, since a plurality of papermaking sludge papermaking bodies are laminated with the raw material solution 14 interposed therebetween, a multilayer hardened body which does not cause peeling can be manufactured.

The pressure press is preferably performed at 10 to 250 kg / cm ² . If the pressure pressing is performed at less than 10 kg / cm ² , the required strength cannot be obtained. On the other hand, 2
This is because the strength cannot be increased even when pressure-pressed over 50 kg / cm ² , and the press machine becomes large in size and expensive.

In this embodiment, a plurality of papermaking sludge papermaking products obtained by papermaking a raw material solution using a wire cylinder (draft body) are laminated. Since it is inefficient to obtain a thick paper product by paper making, a thin paper product is efficiently made from papermaking sludge and laminated to produce a hardened product having the required strength and thickness. This allows
Efficiently mass-produce hardened products from papermaking sludge.

Further, in the manufacturing method of this embodiment, the papermaking sludge is formed to have a thickness of 20 mm or less, so that the papermaking sludge is efficiently made into paper and laminated to produce a cured product having a required strength and thickness. To do. Therefore, it becomes possible to efficiently mass-produce a cured body from the papermaking sludge.

In this embodiment, the paper-making body 26 is laminated while alternately inverting the laminated surface. That is, since the paper products 26 are laminated while the directions of warpage are reversed,
The cured body 1 formed by laminating 6 does not warp and delamination does not occur. Also, the uppermost and lowermost papermaking products are laminated so that the exposed surface is the surface that is in contact with the rotating drum and the uneven surface that is in contact with the conveyor belt 32 made of felt is inside. The surface of the cured product can be made smooth.

Further, in this embodiment, since the flocculant is added to the raw material solution containing the papermaking sludge to cause the flocculation, the hardened body 1 having a uniform specific gravity (range 1.2 to 1.3) is mass-produced from the papermaking sludge. can do. Further, in this embodiment, since the stacking is performed in the female die 54, it is not necessary to transfer the stacked paper products, which is suitable for mass production. In the present embodiment, the layers are stacked in the mold 54, but it is also possible to transfer them into the mold after stacking.

Pressure dehydration and drying with the above press machine 50,
After lowering the water content, the dryer 60 shown in FIG. 3 is used to completely dehydrate and proceed the curing reaction. Dryer 60
Includes an electric heater 62 and a fan 64, and performs drying at a temperature of 80 to 200 ° C. The dryer 60 has an electric heater 62.
Alternatively, an infrared heater, steam, sun dryer or the like can be used instead.

The cured body 1 that has undergone the drying step is further conveyed and cut into a predetermined size by a cutting machine (not shown).
The cutting is performed with a cutter or a saw arranged on the conveyor. Finally, the cut composite cured body 1 is inspected for warp or the like by an inspection machine (not shown). As an inspection machine,
An X-ray sensor, an infrared sensor, etc. can be used. Further, the presence or absence of cracks or cracks may be inspected with an image processing device or the like.

Here, the relationship between the stacking direction (bonding direction) of the paper product and the occurrence of delamination will be described with reference to FIGS. 10 and 11. The right side of FIG. 10 (A) shows a case where the papermaking product 26 is inverted and the felt contact surface side of the conveyor belt is attached. Here, the papermaking body 26
Has a residual stress when wound on the cutting rotary drum 30 shown in FIG. 3, and is warped along the winding direction even after cutting. The left side of the figure shows a cross section of the laminated papermaking body 26,
The unevenness in the figure indicates the felt contact surface. In this embodiment, the laminating direction of FIG. 10 (A) is adopted.

FIG. 10 (B) shows a case where the papermaking product 26 is laminated without being inverted. In addition, FIG.
Shows the case where the papermaking body 26 is inverted and bonded to the cutting rotary drum contact surface side.

FIG. 11 is a chart showing the relationship between the orientation of the papermaking product and the occurrence of delamination, and the relationship between the pressure and strength of the press. In the figure, the coating amount represents the coating amount of the raw material solution 14 between the paper products, the pressure represents the pressure in the press machine, the time represents the pressurizing time, and the density represents the density before drying. It is the density of the cured product, and the maximum load indicates the load that the cured product can withstand after drying, that is, the strength. The water content is the value after pressurization. Shrinkage thickness indicates shrinkage in the thickness direction, shrinkage length indicates shrinkage in the length direction, and shrinkage width indicates shrinkage in the width direction. Here, five paper products are laminated, and the number of peeling layers is the number of peeled layers in five sheets, the number of peeling sides is the number of peeling in four corners, and the peeling length. Indicates the total extension of the peeled portion.

First, it can be seen that the maximum load can be increased by increasing the pressure. In addition, as the direction of stretching, FIG.
It is understood that delamination can be completely prevented by adopting “A” shown in (A) and applying a pressure of 60 kg / cm ² (No.
9). In this embodiment, since the papermaking sludge is used as a raw material, the shrinkage rate is large, and during drying, the residual stress when wound on the cutting rotary drum 30 acts and peeling easily occurs, Peeling can be prevented by inverting and pasting the paper product. In this embodiment, 1
Although the paper product was inverted for each layer, warping and delamination can be prevented by inverting and stacking every two layers or every three layers.

An example of analysis of the composite cured product obtained in the above-mentioned steps using a fluorescent X-ray analyzer (RIX2100 manufactured by Rigaku) is shown below.

Example 1 It was found to have the following composition in terms of oxide. The pulp was calcined at 1100 ° C. and the weight loss was measured. Serial Pulp: 51.4 wt%, SO _3: 0.5 wt% SiO _2: 24.2 wt%, P ₂ O _5: 0.2 wt% Al ₂ O _3: 14.0 wt%, Cl: 0 0.2% by weight CaO: 8.0% by weight, ZnO: 0.1% by weight MgO: 1.4% by weight, others: Trace TiO ₂ : 1.0% by weight,

Next, a method for manufacturing a cured product and an apparatus for manufacturing a cured product according to the second embodiment of the present invention will be described with reference to FIG. The second embodiment is almost the same as the first embodiment except for the cutting method and stacking direction of the paper product.
Therefore, the description is omitted except for the cutting direction and the stacking direction. In the above-described first embodiment, the papermaking product 26 has a size of 1 m × 2.
was cut into m. On the other hand, in the second embodiment, the cutter 26 cuts the papermaking product 26 into 1 m × 1 m.
When the papermaking product 26 is placed on the reversing plate 46 of the reversing device 40 by the conveyor 42 from the belt conveyor 38, the papermaking product 26 is twisted 90 degrees in the horizontal direction before being placed. That is, when stacking the paper products, the wire cylinders 22A, 22B, 22
The transfer direction from C to the conveyor belt 23 is shifted. The paper product 26 has a difference in strength along the transfer direction to the conveyor belt 23. Specifically, assuming that the strength when bending is applied along the transfer direction is 1, the strength in the direction perpendicular to the transfer direction is about 0.8. In the second embodiment, the papermaking body 2
When 6 is laminated, the cured product having uniform strength is manufactured by stacking so that the transfer direction to the conveyor belt 23 is shifted.

Example 2 1500 g of unsintered papermaking sludge (papermaking sludge "fine sludge" of fine paper for OA equipment of Maki Papermaking Co., Ltd. handled by Maruto Kiln Co., Ltd .: solid content 51% by weight, water content 49% by weight)
Prepared. This was made into paper as in Example 1. Also,
X-ray fluorescence analyzer (Rigaku Corporation RIX20
00) was used to analyze the composition. The oxide conversion value is shown below. The amount of pulp was calculated from the amount of weight loss when calcined at 1100 ° C. A peak of calcium carbonate was observed by X-ray. The composition is the amount including calcium carbonate.

Regarding the amount of calcium carbonate, a calibration curve was prepared based on the height of the maximum peak around 2θ = 29 ° on the X-ray diffraction chart and the content of calcium carbonate, and the content of calcium carbonate was measured. Since the calibration curve depends on the device, it is necessary to recreate the calibration curve when performing a diffraction test with a different device. In this application, MiniFlex manufactured by Rigaku Corporation was used. As a result, it was about 11% by weight. Further, from the mapping image of Ca and O of the fluorescent X-ray, the crystal habit of calcium carbonate was presumed to be spindle-shaped.

Composition of the cured papermaking sludge of Example 2 Pulp: 53.1 wt% MgO: 1.3 wt% SiO ₂ : 15.7 wt% SO ₃ : 0.8 wt% Al ₂ O ₃ : 9. 7 wt% P ₂ O _5: 0.8% by weight CaO: 16.3 wt% Cl: 0.3% by weight TiO _2: 1.2 wt% ZnO: 0.6 wt% FeO: 0.2 wt% other Very small amount

Example 3 1500 g of unsintered papermaking sludge (papermaking sludge "fine sludge" of fine paper for OA equipment of Maki Papermaking Co., Ltd. handled by Maruto Kiln Co., Ltd .: 51% by weight of solid content, 49% by weight of water)
73 g of spindle-shaped light calcium carbonate (average diameter 2 μm, Tamapearl TP-121, Okutama Kogyo Co., Ltd.) was added. This was made into paper as in Example 1.

Composition of cured papermaking sludge of Example 3 Pulp: 50.4% by weight MgO: 1.2% by weight SiO ₂ : 14.9% by weight SO ₃ : 0.7% by weight Al ₂ O ₃ : 9. 2% by weight P ₂ O ₅ : 0.7% by weight CaO: 20.6% by weight Cl: 0.3% by weight TiO ₂ : 1.0% by weight ZnO: 0.6% by weight FeO: 0.2% by weight Very small amount

Example 4 1500 g of unsintered paper-making sludge (paper-made sludge "fine sludge" of solid wood of 51% by weight of solid content, moisture content of 49% by weight of fine-grained paper for OA shaving machine of Maki Papermaking Co., Ltd. handled by Maruto Kiln Co., Ltd.)
219 g of columnar light calcium carbonate (average diameter 2 μm, Tamapearl TP-123, Okutama Kogyo Co., Ltd.) was added. X-ray fluorescence analyzer (trade name R manufactured by Rigaku
The composition was analyzed using IX2100). The content of calcium carbonate was measured. As a result, it was about 30.8% by weight.

Composition of cured papermaking sludge of Example 4 Pulp: 45.7 wt% MgO: 1.1 wt% SiO ₂ : 13.5 wt% SO ₃ : 0.7 wt% Al ₂ O ₃ : 8. 4% by weight P ₂ O ₅ : 0.7% by weight CaO: 27.9% by weight Cl: 0.3% by weight TiO ₂ : 1.0% by weight ZnO: 0.5% by weight FeO: 0.1% by weight Very small amount

Example 5 103 parts by weight of a calcined product of papermaking sludge (trade name "Cyclone ash" manufactured by Maruto Kiln Co., Ltd.) and 1209 parts by weight of the unsintered papermaking sludge of Example 1 were kneaded. Then, a composite cured product was produced in the same manner as in Example 1. The composition of the calcined sludge was measured by a fluorescent X-ray analyzer (RIX manufactured by RIX
2100) and analyzed in terms of oxides. The specific gravity was 0.9.

(Calcined product of papermaking sludge) Composition of calcined product of papermaking sludge SiO ₂ : 34.1 wt% MgO: 6.0 wt% Al ₂ O ₃ : 20.7 wt% P ₂ O ₅ : 2.7 % By weight Fe ₂ O ₃ : 12.4% by weight TiO ₂ : 1.0% by weight CaO: 21.3% by weight SO ₃ : 0.5% by weight ZnO: 0.1% by weight Cl: 0.2% by weight Very small amount

Example 6 Ten pieces of core paper impregnated with phenol resin were laminated on kraft paper having a basis weight of 80 g / cm ² , and the temperature was 140 ° C. and 80 kg.
A pressure was applied at / cm ² to obtain a decorative plate. This decorative plate was adhered to both surfaces of the cured product of Example 1 with a vinyl acetate adhesive.

Example 7 To the papermaking sludge having the composition of Example 2 was added 10% by weight of Portland cement. The composition of the cement SiO _2: 22.2 wt% SO _3: 1.6 wt% Al ₂ O _3: 5.1 wt% MgO: 1.4 wt% CaO: 65.1 wt% FeO: 3.2 wt% Other traces

Example 8 3020 parts by weight of unsintered papermaking sludge (low quality paper for OA equipment of Nakamura Papermaking Co., Ltd. handled by Maruto Kiln Co., Ltd .: solid content 34% by weight, water content 66% by weight) was prepared. Next, using 2N hydrochloric acid aqueous solution, acid cleaning is performed to almost completely remove the Ca component,
This was designated as A.

A pulp: 51.2 wt% MgO: 1.6 wt% SiO ₂ : 18.6 wt% SO ₃ : 3.5 wt% Al ₂ O ₃ : 22.3 wt% P ₂ O ₅ : 0 .3 wt% CaO: 0.0 wt% Cl: 0.1 wt% ZnO: 0.2 wt% Other traces

[0113] Further, the papermaking sludge of the ink jet printer paper of Maki Paper Co., Ltd. handled by Maruto Kiln Co., Ltd .; solid content 51% by weight, water content 49% by weight was designated as B. B Pulp: 21.8 wt% SiO _2: 4.6 wt% Al ₂ O _3: 7.5 wt% P ₂ O _5: 0.1 wt% CaO: 65.0 wt% Na ₂ O: 0.2 Weight% SO ₃ : 0.2 weight% Other The amount of trace calcium carbonate was 55 weight%.

In addition, the papermaking sludge of the ink jet printer paper of Maki Paper Co., Ltd. handled by Maruto Kiln Co., Ltd .: 51% by weight of solid content, 49% by weight of water, and 10% by weight of calcium carbonate (cubic shape) was added to obtain C. And C pulp: 15.0% by weight SiO ₂ : 2.6% by weight Al ₂ O ₃ : 5.5% by weight P ₂ O ₅ : 0.1% by weight CaO: 75.0% by weight Na ₂ O: 0.2 Weight% SO ₃ : 0.2 weight% Other The amount of trace calcium carbonate was 65 weight%.

A sample was prepared by appropriately mixing A, B and C as described above, and a hardened body was manufactured by papermaking in the same manner as in Example 1, and the bending strength, compressive strength and nailability were measured. The results are shown in the graphs of FIGS. Here, FIG. 15 shows Ca
The relationship between O / SiO ₂ and compressive strength is shown, with the vertical axis representing compressive strength (Kg / cm ² ) and the horizontal axis representing the ratio of CaO / SiO ₂ . FIG. 16 shows the relationship between CaO / Al ₂ O ₃ and compressive strength. The vertical axis represents compressive strength (Kg / cm ² ) and the horizontal axis represents CaO /
The ratio of Al ₂ O ₃ is taken. FIG. 17 shows the relationship between the content of CaO and the flexural strength / compressive strength. The vertical axis represents the flexural strength / compressive strength (Kg / cm ² ) and the horizontal axis represents the content of CaO (%). FIG. 18 shows the relationship between the content of CaO and the nail pull-out strength, and the vertical axis shows the nail pull-out strength (Kg
/ A cm ²⁾ are taking the content of CaO in the horizontal axis (%).
As shown in FIG. 15, in the cured body, the amounts of Ca, Al, and Si are converted into CaO, Al ₂ O ₃ , and SiO ₂ , respectively, and Ca
A high compressive strength is exhibited when the O / SiO ₂ ratio is 0.2 to 7.9. On the other hand, as shown in FIG. 16, the cured product exhibits high compressive strength when the ratio of CaO / Al ₂ O ₃ is 0.2 to 12.5.

Comparative Example 1 1512 g of unsintered papermaking sludge (Maruto Kiln Co., Ltd. trade name "green sludge": solid content 34% by weight, water content 66% by weight)
Prepared. Then, the papermaking sludge is 1800 mm x
It was poured into a mold having an area of 1000 mm. Then,
Insert stainless steel plate, punching metal plate, non-woven fabric, and insert 45 push rods with 190 mm square cross section, press for 5 minutes while applying pressure of 60 kgf / cm ² for 30 minutes pressurization time, and press 10 mm thick. It was a sheet-shaped molded body. This sheet-shaped molded body was heated at 100 ° C. to obtain a plate-shaped composite cured body. The specific gravity was 1.2.

The thus-obtained composite cured product was analyzed using a fluorescent X-ray analyzer (RIX2100 manufactured by Rigaku), and it was found that it had the following composition in terms of oxide. The pulp was calcined at 1100 ° C. and the weight loss was measured.

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 0.2% by weight CaO: 8.0% by weight Cl: 0.2% by weight TiO ₂ : 1.0% by weight ZnO: 0.1% by weight Others A trace amount of calcium carbonate was 9.8% by weight.

Comparative Example 2 The papermaking sludge of Example 1 was washed with 1N hydrochloric acid to remove calcium carbonate, and then 84 g of spherical calcium carbonate (average diameter 2 μm, C-90, Okutama Kogyo Co., Ltd.) was added. It is about 11% by weight based on the solid content. However, in the papermaking, almost no calcium carbonate could be incorporated into the cured product.

Comparative Example 3 55% by weight of Portland cement was added to the papermaking sludge of Example 2.

Comparative Example 4 In Comparative Example 4, dewatering suction was not performed by the conveyor belt.

The composite hardened bodies obtained in the above Examples and Comparative Examples were tested for bending strength, compressive strength, workability and nailability, fracture toughness, and abrasion resistance. The results are shown in Table 1. The test method has a bending strength of JI.
S A 6901 and compressive strength JIS A 54
It measured according to the method prescribed | regulated in 16 respectively. The workability was judged by cutting with a circular saw for woodwork. Furthermore, regarding nailability, diameter 4 mm, length 5
A 0 mm nail was struck and the presence or absence of cracks was examined. Fracture toughness value is Vickers hardness tester (Akashi Seisakusho MVK-
It was calculated from the length of the crack generated by pressing the indenter according to D). The Young's modulus was calculated from the curve of the bending fracture test and was 1.4 to 2.7 kgf / cm ² , and this value was used. In addition, Munsell color chart was used for the lightness.

[0123]

[Table 1] Bending strength Compressive strength Workability Nailability Fracture toughness Lightness kg / cm ² kg / cm ² MPa · m ^1/2 Example 1 330 850 Machinable None 3.3 7 Example 2 335 860 Machinable None 3.3 7 Example 3 340 865 Machinable No 3.3 3.3 7.5 Example 4 350 870 Machinable None 3.2 7.5 Example 5 330 850 Machinable None 3.2 7 Example 6 330 850 Machining Yes No 3.3 7 Example 7 310 800 Machinable No 3.1 6 Comparative Example 1 300 850 Machinable None 3.0 4.5 Comparative Example 2 280 790 Machinable None 3.5 4 Comparative Example 3 180 300 300 Machining No Yes 2.5 4 Comparative Example 4 310 850 Machinable No 3.0 3.0

Regarding the composite cured product of Example 1, X
The crystal structure was confirmed by line diffraction. The X-ray diffraction chart is shown in FIGS. 12 and 13. In addition, X-ray diffraction is
Cu was used as a target by using MiniFlex manufactured by igaku. A gentle undulation (halo) is observed in the region of 2θ = 15 ° to 30 °, and a peak showing a crystal structure is also observed, which shows that the crystal structure is mixed in the amorphous structure. In addition, a calcium carbonate crystal (Calsite) was identified from the peak.

The lightness increases as the amount of cement and the amount of CaO increase. Further, the papermaking method has higher brightness than the pressing method. In addition, calcium carbonate with horns is easier to incorporate by the papermaking method, and the brightness can be increased.

A composite building material will be described below as one application example of the composite cured body 1. That is, as shown in FIG. 19, in a composite building material in which a reinforcing layer 6 is formed on at least one surface of a core material 5, both surfaces in the illustrated example, a composite cured body produced by the method of the present invention on the core material 5. Apply 1. That is, by using the core material 5 as the composite cured body 1 produced by the method of the present invention, even when a tensile force is applied to the core material, the core material itself has excellent bending strength, and Combined with the fact that the reinforcing layer is provided on the surface, the structure does not easily break.
Further, even if pressure is locally applied to the surface, no dent or dent occurs.

Furthermore, when this composite building material is used, since a decorative layer such as a coating, a decorative board and a decorative veneer is provided on the reinforcing layer 6, the impact resistance is improved, and a dent or the like is formed. Is less likely to occur, and the decorative surface is not distorted by scratches and the design is not deteriorated.

Further, 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 as the resin 6a. That is, unlike a thermoplastic resin, a thermosetting resin has excellent fire resistance and does not soften even at high temperatures, so that the function as a reinforcing layer is not lost. As the thermosetting resin, phenol resin, memelamine resin, epoxy resin, polyimide resin, urea resin and the like are suitable. Then, in order to impart sufficient rigidity, impact resistance, and higher fire resistance to the reinforcing layer, the content of the thermosetting resin in the reinforcing layer is preferably 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 material 6b. This is because it is possible to improve the strength of the reinforcing layer 6 and reduce the coefficient of thermal expansion. As the inorganic fiber, it is possible to use one or more of glass fiber, rock wool, ceramic fiber, glass fiber chopped strand mat, glass fiber roving cloth, glass fiber continuous strand mat, and glass fiber paper, which is low cost and heat resistant. It is preferable in terms of excellent properties and strength. This fiber base material is formed by forming discontinuous fibers into a mat shape, or by cutting continuous long fibers into 3 to 7 cm into a mat shape (so-called chopped strand mat), and a sheet shape by dispersing with water. It is possible to apply the one that has been plowed, the one that is formed by spirally laminating continuous long fibers into a mat, or the one that is obtained by weaving continuous long fibers.

Further, the reinforcing layer has a thickness of 0.1 mm to
It is desirable to set it to 3.5 mm. This is because when the content is set in this range, sufficient rigidity and impact resistance can be obtained, and high workability can be maintained. In addition, 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 may be added to the reinforcing layer. Although the reinforcing layer is provided here, it is also possible to coat the surface with a resin or the like so that the cured body does not absorb moisture.

[Brief description of drawings]

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

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

FIG. 3 is a conceptual view of a cured body manufacturing apparatus according to a first embodiment of the present invention.

4A and 4B are conceptual diagrams of a raw material adjusting mechanism.

FIG. 5 is a conceptual diagram of a papermaking mechanism.

6A, 6B, and 6C are explanatory views of the operation of the cutting rotary drum.

7 (A), (B), and (C) are explanatory views of the operation of the reversing device.

8A, 8B, and 8C are explanatory views of the operation of the press machine.

9A, 9B, and 9C are explanatory views of the operation of the press machine.

FIG. 10A, FIG. 10B, and FIG. 10C are explanatory views of the pasting direction of the paper product.

FIG. 11 is a chart showing the relationship between the orientation of the papermaking product and the occurrence of delamination, and the relationship between the pressure and strength of the press machine.

FIG. 12 is an X-ray diffraction chart of the composite cured product of Example 1.

13 is an X-ray diffraction chart of the composite cured product of Example 1. FIG.

FIG. 14 is a conceptual diagram of an apparatus for manufacturing a cured body according to a second embodiment of the present invention.

FIG. 15 is a graph showing the relationship between CaO / SiO ₂ and compressive strength.

FIG. 16 is a graph showing the relationship between CaO / Al ₂ O ₃ and compressive strength.

FIG. 17 is a graph showing the relationship between the content of CaO and bending strength / compressive strength.

FIG. 18 is a graph showing the relationship between the content of CaO and the nail pull-out strength.

FIG. 19 is a schematic cross-sectional view of a composite building material using the composite cured product of the present invention.

[Explanation of symbols]

1 Composite cured product 2 Amorphous body 3 fibrous material 4 Inorganic powder 5 core material 6 Reinforcement layer 10 Raw material adjustment mechanism 14 Raw material solution (slurry) 15 Dehydration container 16 filters 17 Vacuum pump 18 chest tank 20 Paper making mechanism 21A, 21B, 21C bat 22A, 22B, 22C Wire cylinder 23 Conveyor belt 24 suction box 26 Paper products 30 Rotary drum for cutting 31 piano wire 32 Storage groove 33 storage groove 36 cutters 38 Belt conveyor 40 Reversing device 42 Conveyor 44 tables 46 Inversion plate 50 press machine 52 Male 52a through hole 54 female 54A recess 54a through hole 56 curtain coater 60 dryer

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshihiro Nomura 2-1-1 Kanda-cho, Ogaki-shi, Gifu Ibiden Co., Ltd. (56) References JP-A-49-114628 (JP, A) JP-A-11- 279992 (JP, A) JP 9-309723 (JP, A) JP 6-56422 (JP, A) JP 58-70796 (JP, A) JP 5-71097 (JP, A) JP-A-10-121400 (JP, A) JP-A-48-26265 (JP, A) Actually open 1-157198 (JP, U) Actually open 57-171612 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) D21H 11/00-27/42 D21J 1/00-7/00

Claims (3)

(57) [Claims] 1. A papermaking sludge made by papermaking and hardened, containing an organic fibrous substance made of a polysaccharide and calcium carbonate in an inorganic amorphous substance made of an oxide of each of Si, Al and Ca. In the cured product, the amounts of Ca, Al, and Si in the cured product are Ca
O, Al ₂ O ₃ , and SiO ₂ have a CaO / SiO ₂ ratio of 0.2 to 7.9 and a CaO / Al ₂ O ₃ ratio of 0.2.
To 12.5, and the lightness of the cured product is N5 or more in a value based on the regulation of JIS Z 8721, which is a cured product of papermaking sludge. 2. The hardened body of papermaking sludge according to claim 1, wherein the crystal habit of the calcium carbonate is at least one form selected from a spindle shape, a horn shape, a thin table shape, a cube or a column shape. 3. The cement content of the papermaking sludge is
The hardened body of the papermaking sludge according to claim 1, which is 0 or 30% by weight or less.