WO2001042565A1 - Article composite durci et materiau de construction composite - Google Patents

Article composite durci et materiau de construction composite Download PDF

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Publication number
WO2001042565A1
WO2001042565A1 PCT/JP2000/003788 JP0003788W WO0142565A1 WO 2001042565 A1 WO2001042565 A1 WO 2001042565A1 JP 0003788 W JP0003788 W JP 0003788W WO 0142565 A1 WO0142565 A1 WO 0142565A1
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WIPO (PCT)
Prior art keywords
composite
cured product
weight
composite cured
inorganic
Prior art date
Application number
PCT/JP2000/003788
Other languages
English (en)
Japanese (ja)
Inventor
Yoshimi Matsuno
Tetsuji Ogawa
Kenji Satou
Toshihiro Nomura
Original Assignee
Ibiden Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/JP1999/006970 external-priority patent/WO2000036242A1/fr
Priority claimed from PCT/JP1999/006968 external-priority patent/WO2000036218A1/fr
Priority claimed from PCT/JP1999/006969 external-priority patent/WO2000035820A1/fr
Application filed by Ibiden Co., Ltd. filed Critical Ibiden Co., Ltd.
Publication of WO2001042565A1 publication Critical patent/WO2001042565A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/04—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
    • E04C2/06—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres reinforced
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes

Definitions

  • 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.
  • Japanese Patent Application Laid-Open No. 7-41050 discloses that pulp residue (scum) generated after the production of paper is effectively used as a building panel.
  • inorganic materials such as silica and alumina obtained by firing scum are mixed with cement, fiber and water, and pressed against a porous iron plate.
  • Japanese Patent Application Laid-Open No. 10-218643 discloses a cement admixture containing waste slag.
  • Japanese Patent Application Laid-Open No. 10-218643 has a problem that it has excellent compressive strength but low flexural strength, and this technology is used for column materials and plate materials for building materials. To Requires higher bending strength.
  • any technology uses cement, so it is not possible to drive nails, etc., and forcing it has the disadvantage of causing cracks.
  • the present invention solves the above-mentioned problems and, in using industrial waste, provides a composite cured product having improved bending strength without impairing workability and productivity, and a composite cured product.
  • the purpose is to make proposals on the composite building materials used. Disclosure of the invention
  • the gist configuration of the present invention is as follows.
  • a composite cured product characterized in that it has inorganic crystals containing Ca in an inorganic amorphous material and a mixture of fibrous materials.
  • a composite cured product in which a fibrous material is mixed in an inorganic amorphous material containing at least Si, A1, and Ca, wherein the amount of Ca is composite cured in terms of Ca0.
  • a composite cured product characterized in that it is at least 3% by weight and less than 6% by weight based on the total weight of the body.
  • a composite building material comprising a core material and paper adhered to at least one surface thereof, wherein the composite material is obtained by applying the composite cured product according to any one of 1 to 12 to the core material.
  • the present invention is characterized in that the inorganic amorphous body has an inorganic crystal containing Ca and that a fibrous material is mixed. With such a configuration, the inorganic crystal containing Ca can prevent the crack from developing, and can improve the strength by increasing the hardness and density to improve the compressive strength.
  • the content of the inorganic crystal containing Ca is preferably 3% by weight or more and 50% by weight or less based on the composite. This is because the strength can be increased.
  • the fibrous material is contained in the inorganic amorphous material containing at least Si, A1, and Ca.
  • the amount of the C a is a 3% to 6 3 weight 0/0 of the total weight of the composite cured body C a 0 conversion. If the amount is less than 3% by weight, the fracture toughness cannot be increased, whereas if it exceeds 63% by weight, the fracture toughness cannot be increased.
  • the amount of the C a is desirably in the C a 0 6 weight against the total weight of the composite cured body in terms 0 / 0-6 3 wt 0/6. This is because the strength of the composite can be increased.
  • the amount of Ca is desirably 3% by weight or more and less than 6% by weight based on the total weight of the composite cured body in terms of Ca 0. This is because the fracture toughness value can be increased. When a crystal is included, the fracture toughness value seems to be affected by the balance between the crystalline and amorphous regions. Region of the crystalline inorganic amorphous material in is considered possible to increase the breaking toughness' 1 1 raw value by distributing.
  • a composite cured product in which a fibrous material is mixed in an inorganic amorphous material containing at least Si, A1, and Ca, wherein the amounts of Ca and A1 are each C A_ ⁇ , the ratio of C a O / a 1 2 0 3 in terms of a 1 2 0 3 exceeds 0.2. If it is less than 0.2, a Ca-based crystal is not formed, and the fracture toughness and strength are not sufficient.
  • FIG. 1 schematically shows the structure of the composite cured product of the present invention.
  • the composite cured product 1 is characterized in that inorganic crystals containing Ca are present in the inorganic amorphous material 2 and fibrous materials 3 are mixed in the inorganic amorphous material 1. .
  • the presence of the inorganic crystal improves the compressive strength, the bending strength, and the crack resistance. The reason for this is not clear, but the crystals hinder crack propagation, increase the hardness and density to make cracks less likely to occur, and play the role of struts for compressive force. Then
  • Such crystals Chaleni te, syn, Anorthi te , Melitite, Gehlen ite - synthetic, tobermor i te, xonotl lie, and ettringi te, CaO, and there are crystal such as C aC0 3 (Calcite).
  • the content of the crystal is desirably 3 to 50% by weight based on the total weight of the composite cured product. The reason for this is that if the number of crystals is too small, the above effect cannot be obtained, while if it is too large, the strength is reduced.
  • the A 12 0 3 -C a 0-based crystalline compound Calcium Aluminate, CaO-S i 0 2 based crystalline compound of Calcium Silicate A 1 2 0 3 - .
  • S I_ ⁇ 2 one C A_ ⁇ system crystalline compound Gehlen ite, syn, a Anorthi te, also a 1 2 0 3 one S i 0 2 - Ca_ ⁇ - crystalline compound of MgO system is Mel ite, Gehleni te-synthe tic .
  • calcium carbonate may be added as a crystal.
  • Carbonic acid calcium itself is not a strength-expressing substance, but it is thought that the inorganic amorphous material surrounding the carbonic acid calcium calcium contributes to the improvement of the strength by preventing cracks from developing. However, it is presumed that it will play the role of a support for the compression force.
  • the content of the calcium carbonate is desirably 48% by weight or less based on the total weight of the composite cured product. The reason for this is that if it exceeds 48% by weight, the flexural strength decreases. Further, it is desirable that the content be 0.1% by weight or more. If the content is less than 0.1% by weight, it does not contribute to improving the strength.
  • the inorganic amorphous material used in the present invention is not particularly limited, and Si, Al,
  • Inorganic amorphous bodies of various oxides containing two or more elements selected from Ca, Na, Mg, P, S, K, Ti, Mn, Fe, and Zn can be used.
  • the inorganic amorphous body composed of two or more kinds of oxides is an oxide (1) -oxide (2) ⁇ -oxide (n) system (where n is a natural number, The oxide (1), the oxide (2), and the oxide (n) are different oxides).
  • the inorganic amorphous substance is an amorphous compound formed by a solid solution or hydration reaction of two or more oxides.
  • such inorganic amorphous compounds can be used to determine the constituents of oxides (ASi, Ca, Na, Mg, P, S, K, Ti, Mn, Fe, Zn). 2 or more selected) are confirmed, and in the analysis chart by X-ray diffraction, halos are observed in the range of 2 °: 15 ° to 40 °.
  • Halo is a gradual undulation of the intensity of X-rays and is observed as a broad swell on the X-ray chart. The halo has a half width of 26: 2 ° or more.
  • the inorganic amorphous body 1 and the inorganic crystal body interact with each other to become a strength-producing substance, and the fibrous material 3 is dispersed in the inorganic amorphous body 2 to reduce the fracture toughness value.
  • the bending strength value ⁇ the impact resistance can be improved.
  • the amorphous body has pores more easily than the crystalline body, and the specific gravity can be easily adjusted.
  • the amorphous body has the advantage that not only is it possible to obtain a homogeneous hardened body without anisotropy in strength, but also because it is an amorphous body, sufficient strength can be obtained at a low density.
  • 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.
  • a 12 ⁇ 3, S i 0 2, Ca_ ⁇ , Na 2 0, Mg_ ⁇ , P 2 ⁇ 5, S_ ⁇ 3, K 2 0, T I_ ⁇ 2, Mn_ ⁇ , is preferably selected from F e 2 0 3 and Z n 0.
  • a 1 2 ⁇ 3 -S i 0 2 - CaO system or A 1 2 0 3 _S i 0 2 - CaO- consists oxide inorganic amorphous substance, or complexes of these inorganic amorphous material Is the best is there.
  • the oxide in the latter inorganic amorphous material is A 1 2 0 3, 1 or more S i 0 2 metal excluding and C A ⁇ and / or oxides of non-metallic.
  • the inorganic amorphous body composed of A l 2 0 3 -S i 0 2 -Ca_ ⁇ system, A 1 2 ⁇ 3, S i 0 2 and C a solid-together all or part of the components of the 0 It is a compound having an amorphous structure formed by dissolution or hydration. That, A l 2 ⁇ 3 and S I_ ⁇ 2, S I_ ⁇ 2 Ca_ ⁇ , A 1 2 0 3 and CaO and A l 2 ⁇ 3, S i ⁇ 2 and solid solution or hydration in combination CaO, It is considered to include any of the compounds formed by the reaction or the like.
  • a 1 2 0 3, S I_ ⁇ 2 and at least one oxide of pressurized example was the system in addition to CaO, that is A 1 2 0 3 -S i 0 2 -CaO- consists oxide inorganic amorphous body, in addition to the combination of the above a 12 ⁇ 3 -S i 0 2 -Ca_ ⁇ system, a 1 2 ⁇ 3 oxide, S i 0 2 and oxide, CaO oxide, a 1 2 0 3 , S i 0 2 and oxides, combinations of S i 0 2, C A_ ⁇ and oxides, a 1 2 0 3, CaO and oxide, and a 1 2 0 3, S I_ ⁇ 2, CaO and oxides It is considered to include any of the compounds formed by solid solution or hydration reaction at the same time.
  • the oxide is 2 or more, i.e., A 1 2 0 3 - S i 0 2 -CaO- oxide (1) ⁇ ⁇ ⁇ monoxide of (n) based (n is a natural number of 2 or more) the inorganic non If it is a crystalline body, these oxides, for example, oxide (1), oxide (2) ⁇ , oxide (n) (n is a natural number of 2 or more, and oxide (n) is n means respectively if the values differ oxide, and a 1 2 0 3, S i 0 2, in which except for the C a 0) of the solid solution or hydrated with two or more combinations selected from each compounds formed by reacting the like, a 1 2 0 3, S i 0 2, solid in two or more combinations selected from C A ⁇ At least one compound selected from oxide (1), oxide (2), oxide (n) (n is a natural number of 2 or more) If contemplated to include either the a 1 2 0 3, S i 0 2, C a 0 from
  • Such inorganic amorphous compounds were analyzed by A1, Si, Ca, and the elements (Na, Mg, P, S, K, Ti, Mn, Mn, At least one selected from Fe and Zn) was confirmed, and a halo was observed in the range of 2 °: 15 ° to 40 ° in the analysis chart by X-ray diffraction. Halo is a gradual undulation of the intensity of X-rays, and is observed as a prominent peak on the X-ray chart.
  • Such an inorganic amorphous compound can be said to be an inorganic amorphous material containing at least A1, Si, and Ca.
  • a 1 2 ⁇ 3, S i 0 2 and C A_ ⁇ an oxide to be combined, one or is 2 or more, except for A l 2 0 3, S i 0 2, C A_ ⁇ available oxides of metals and / or non-metal, chosen for example Na 2 0, MgO, P 2 Os, S0 3, K 2 ⁇ , T i 0 2, Mn_ ⁇ from F e 2 0 3 and Z n 0 be able to. This selection can be made based on the properties expected of the composite cured product.
  • Na 2 ⁇ or K 2 ⁇ can be removed with an alkali or the like, if removal treatment is performed prior to plating, the surface of the composite hardened body becomes rough and the anchor will become rough. Can work.
  • MgO is, A 1 2 ⁇ 3, as a solid solution with S i 0 2, CaO contributes to strength development, greatly improve the bending strength Ya impact resistance.
  • S0 3 is suitable for antibacterial building material has a bactericidal action.
  • T i 0 2 together with a whitish coloring agent, since it acts as a photooxidation catalyst It has the unique effect that it can be used as a building material with self-cleaning power, which can forcibly oxidize attached organic pollutants and can be cleaned only by irradiating light, or as various filters and reaction catalysts.
  • M n 0 is dark color colorant
  • F e 2 0 3 is colorant bright color
  • ZnO is useful as a colorant whitish.
  • These oxides may be present alone in the inorganic amorphous body.
  • composition of the inorganic amorphous body each A 1 2 ⁇ 3, S I_ ⁇ 2 and C a 0 to conversion calculated, A l 2 0 3: 5 ⁇ 5 1 relative to the total weight of the composite hardened product wt%, S i 0 2: composite cured of 8-5 3 wt% and C aO-relative to the total weight: 3-6 3% by weight relative to the total weight of the composite hardened product, and the total thereof 1 0 It is preferable to contain it in a range not exceeding 0% by weight.
  • the conversion to Ca_ ⁇ / ratio of S i 0 2, CaO / A 1 2 0 3 to the oxide 0.2 or more preferably, it is desirable that shall exceed 0.2. This is because the greater the amount of Ca, the easier it is to form crystals and the easier it is to improve strength and toughness.
  • 0.2 to 7 the proportion of C aO-/ S I_ ⁇ 2.9 preferably, be a 7.9 hereinafter exceed 0.2, also of C A_ ⁇ / A 1 2 0 3 Adjusting the ratio to 0.2 to 12.5, desirably from 0.2 to 12.5 or less is advantageous for obtaining a cured product having high strength, toughness and strength.
  • a 1 as 2 0 3 oxides other than S i 0 2 and C a 0, Na 2 ⁇ , M g O, P 2 ⁇ 5, S 0 3, K 2 0, T I_ ⁇ 2, Mn_ ⁇ when containing F e 2 0 3 and Zn_ ⁇ , 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.
  • amorphous structure can be confirmed by X-ray diffraction. That is, if a halo is observed in the region of 2 °: 15 ° to 40 ° by X-ray diffraction, it can be confirmed that the material has an amorphous structure.
  • a crystal may be included in the amorphous structure.
  • Gehlenite, syn, Anorthite, Melitite , Gehleni te - synthet IC, tobermori ie, xonot 1 ite, and ettringite, C a O, and C aC0 3 (Calcite) crystals such as may be Mashimashi mixed.
  • These crystals have a force that is not considered to be a strength-expressing substance itself.
  • the hardness and density are increased to improve the compressive strength or to suppress the progress of cracks.
  • the content of the crystal is desirably 0.1 to 50% by weight based on the total weight of the composite cured product. The reason for this is that if the number of crystals is too small, the above effect cannot be obtained, while if the number is too large, the strength is reduced.
  • the content of the crystal is more preferably 3 to 50% by weight based on the total weight of the composite cured product.
  • the A 12 0 3 -C a 0-based crystalline compound Calcium Aluminate, C a 0- S i 0 2 based crystalline compound of Calcium Silicate A 1 2 0 3 one S I_ ⁇ 2 -.
  • C a as crystals, Gehlenite, syn (C a 2 A 12 Rei_7), Melitite-synthetic (C a 2 (M g 0. S A 1 0. S) (S i i. 5 A 1 o. 5 07) ) ⁇ Why Gehl en ite- synthetic (C a 2 (M g 0 .25 A 10. 75) (S i 1. 25 A 10. 75 O 7)), anorthite, ordered (Ca 2 a l 2 S i 2 0 8), a carbonate Chikararu Shiumu (Calcite), may contain.
  • the composite cured product of the present invention preferably has a specific gravity of 0.2 to 2.2.
  • the specific gravity is less than 0.2, the number of pores is too large and the strength of the composite cured product is reduced.
  • the reinforcement effect is relatively reduced, and the strength is also reduced. That is, practical compressive strength and bending strength can be obtained when the specific gravity is in the range of 0.1 to 1.2, and this range can be said to be an advantageous range for obtaining bow strength.
  • the specific gravity is optimally 1.1 to 2.0. This is because the strength can be maximized.
  • the specific gravity refers to the density of a substance when the density of water at 4 ° C is defined as 1.
  • the specific gravity is measured by measuring the volume and weight of the cured product, and calculating by (weight / volume) /0.999973.
  • the specific gravity is preferably from 0.5 to 1.8, and most preferably from 0.7 to 1.4. This is because cracks during nailing can be specifically suppressed in this range. That is, if the specific gravity is less than 0.5, the number of pores is too large and the pores develop cracks. Conversely, if the specific gravity is more than 1.8, the influence of the inorganic amorphous material itself becomes too large, and The reinforcing effect is relatively reduced, the fracture toughness value is reduced, and cracks tend to occur.
  • halogen may be added to an inorganic amorphous material composed of at least two or more types of oxides.
  • This halogen acts as a catalyst for the solid solution and hydrate formation reactions and also acts as a combustion inhibitor. Its content is preferably from 0.1 to 1.1% by weight. This is because if it is less than 0.1% by weight, the strength is low, and if it exceeds 1.2% by weight, harmful substances are generated by combustion.
  • As the halogen chlorine, bromine, and fluorine are preferable.
  • calcium carbonate (C a C 3 : 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 inorganic amorphous material, it contributes to strength improvement by preventing cracks from developing.
  • the content of calcium carbonate is desirably 48% by weight or less based on the total weight of the composite cured product. The reason for this is that if it exceeds 48% by weight, the flexural strength decreases. 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 binder is desirably made of one or both of a thermosetting resin and an inorganic binder.
  • a thermosetting resin at least one resin selected from phenol resin, 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.
  • thermosetting resin for example, at least one thermosetting resin selected from a phenol resin, a melamine resin, an epoxy resin, a urea resin, and a polyurethane resin, It may be applied to the surface.
  • the fibrous material mixed in the inorganic amorphous material may be either organic or inorganic.
  • the organic fibrous material at least one selected from the group consisting of synthetic fibers such as vinylon, propylene and polyethylene, and organic fibrous materials composed of polysaccharides can be used, and organic fibrous materials composed of polysaccharides can be used. It is desirable. This is because, the polysaccharide is because there are OH groups, A 1 2 0 3. Easily combines with S i 0 2 or various compounds of C a 0 by hydrogen bonding.
  • the polysaccharide is desirably at least one compound selected from amino sugars, peruronic acid, starch, glycogen, inulin, lichenin, cellulose, chitin, chitosan, hemicellulose and pectin.
  • organic fibrous material composed of these polysaccharides pulp, pulp grounds, and crushed waste paper such as newspapers and magazines are advantageously suited.
  • the pulp contains about 10 to 30% by weight of lignin in addition to cellulose.
  • the inorganic fibrous material at least one selected from alumina whiskers, SiC whiskers, silica-based ceramic fibers, glass fibers, carbon fibers, and metal fibers can be used.
  • the content of the fibrous material is desirably 2 to 5% by weight.
  • the reason for this is that if the content is less than 2% by weight, the strength of the composite cured product may be reduced, while if it exceeds 75% by weight, fire protection performance, water resistance, dimensional stability, etc. may be reduced.
  • the average length of the fibrous material is desirably 10 to 300 m. If the average length is too short, no entanglement will occur, and if the average length is too long, voids will form and the strength of the inorganic cured product will be reduced.
  • the above composite cured product be obtained by drying and coagulating and hardening industrial waste.
  • the one obtained by drying and coagulating and hardening papermaking sludge (scum) is optimal.
  • paper sludge is pulp residue containing inorganic substances, This is because the material is used as a raw material and the cost is low, which contributes to solving environmental problems.
  • 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.
  • papermaking sludge in addition to pulp, oxides of A and Si, Ca, Na, Mg, P, S, K, Ti, Mn, Fe and Zn, Or a sol-like substance that is a precursor of a compound, a carbonate, a complex compound of these, or an oxide thereof, or a complex thereof, at least one selected from halogen and carbonated calcium, and generally contains water. It is a target.
  • high-quality waste paper contains a large amount of calcium-based crystals such as kaolin and calcium carbonate. Therefore, papermaking sludge containing a large amount of waste paper is suitable.
  • the water content in the papermaking sludge is desirably 20 to 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.
  • the inorganic powder 4 is mixed in the composite hardened body 1 to improve the fire resistance, or to react with the inorganic amorphous body to form a strength-expressing substance, thereby enhancing the strength. This is advantageous for improving the degree of the degree, and by adjusting the amount of the inorganic powder, the specific gravity of the composite cured product can be adjusted.
  • the inorganic powder at least one selected from calcium carbonate, calcium hydroxide, shirasu, shirasu balun, perlite, aluminum hydroxide, silica, alumina, talc, calcium carbonate, and industrial waste powder can be used.
  • the industrial waste powder it is desirable to use at least one type of industrial waste powder selected from calcined powder of papermaking sludge, grinding dust of glass, and grinding dust of silica sand. This is because by using these industrial waste powders, it is possible to realize cost reduction and further contribute to solving environmental problems.
  • the inorganic powder obtained by calcining the papermaking sludge was made from papermaking sludge of 300 to 150 .
  • the inorganic powder thus obtained is amorphous, has excellent strength and toughness, and has a low density, so that it can be reduced in weight by dispersing it in a composite cured product.
  • the powder is advantageous because it certainly contains an inorganic amorphous material.
  • Inorganic powder has a specific surface area, 1. 6 is desirably 1 is 0 O m 2 / g. If it is less than 0.8 m 2 / g, the contact area between the inorganic amorphous material and the inorganic powder becomes small, and the strength decreases.On the other hand, if it exceeds 10 O m 2 / g, crack growth and hardness increase. As a result, the strength is reduced.
  • the inorganic powder desirably contains at least one or more inorganic substances selected from silica, alumina, iron oxide, calcium oxide, magnesium oxide, lithium 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, so that the average particle size is desirably in the range of 1 to 100 m.
  • 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. On the other hand, if the amount of the inorganic powder is too large, it becomes brittle, and in any case, the strength is reduced.
  • a water absorption inhibitor (including a water-repellent agent) may be added.
  • the addition of the water-absorbing inhibitor suppresses the water absorption of the composite cured product, so that a decrease in strength due to water absorption can be avoided.
  • by suppressing the amount of absorbed water it is possible to prevent cracking due to repeated freezing and melting of the absorbed water.
  • a water-absorbing inhibitor including a water-repellent agent
  • a water-absorbing agent in an amount of 0.1% by weight or more, but if it exceeds 10% by weight, the strength of the composite cured product is increased. In order to cause a decrease, 0.1 to 10% by weight is desirable, and 0.2 to 4% by weight is optimal.
  • the water-absorbing agent has a role and an effect of preventing water from entering the composite cured body.
  • rosin-based, paraffin (paraffin wax), reactive sizing agent, stearic acid (Calcium stearate), modified petroleum resin, microwax, silane, 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 absorption inhibitor may be uniformly dispersed in 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 inhibitor is dispersed and molded. Alternatively, a predetermined amount is applied to the surface of the composite cured product using a brush, a roll, a spray, or the like, followed by drying, heat curing, curing, etc. to form a coating film.
  • the composite hardened body according to the present invention is used in various industries, and includes medical materials for artificial limbs, artificial bones, and artificial roots, including new building materials replacing calcium silicate boards, perlite boards, plywood, gypsum boards, and the like. It can be used for electronic materials such as a core substrate of a printed wiring board and an interlayer resin insulating layer.
  • this composite cured body is used for free access floors such as offices, free floors for condominiums, etc., gymnasium walls, soundproof doors, acoustic support plates, anti-fouling materials, exterior materials, soundproof walls, soundproof floors, and roof bases. , Stair steps, concrete formwork, furniture surface materials, table tops, kitchen doors, toilet booths, floor bases, field edges, field edges, body edges, joists, floor joists, vibration damping materials, sound insulation materials, etc. Can be used.
  • the composite cured body 1 of the present invention is applied to the core material 5. It is characterized by becoming. That is, by using the composite material 1 of the present invention as the core material 5, even when a tensile force is applied to the core material, the core material itself can be used. Because of its excellent bending strength, the core is also provided with a reinforcing layer on the surface, so that it is not easily broken. Also, no dents or depressions occur even when pressure is locally applied to the surface.
  • 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. Scratch is less likely to occur, and the decorative surface is not distorted by the scratch 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 high temperatures, so that the function as a reinforcing layer is not lost. Suitable thermosetting resins include phenolic resin, melamine resin, epoxy resin, polyimide resin and urea resin. In order to provide the reinforcing layer with sufficient rigidity, impact resistance, and high fire resistance, the content of the thermosetting resin in the reinforcing layer should be in the range of 10% by weight to 65% by weight. Is desirable.
  • the fiber base material is a non-continuous fiber formed into a mat shape, or a continuous long fiber cut into 3 to 7 cm into a mat shape (a so-called chopped strand mat), which is dispersed in water. It can be applied in the form of a sheet that has been swept into a sheet, a sheet in which continuous long fibers are spirally laminated to form a mat, or a sheet in which continuous long fibers are woven.
  • the thickness of the reinforcing layer is desirably 0.2 mm to 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.
  • aluminum hydroxide, magnesium hydroxide Flame retardants such as rubber, and generally used inorganic binders such as silica sol, alumina sol and water glass may be added.
  • the reinforcing layer contains an elastic polymer. Cracking does not occur from the nail as a starting point even when the nail is hit, and the elastic polymer can secure the frictional force with the nail surface and improve the holding power of the nail.
  • a resin composition for imparting nail strength comprising a thermosetting resin and an elastic polymer
  • the emulsion of the elastic polymer is dispersed in the uncured thermosetting resin liquid.
  • the resin cures, it becomes a structure in which "islands" of elastic polymer are dispersed in the "sea” of the thermosetting resin matrix, ensuring the strength of the resin and imparting toughness. It is.
  • the elastic polymer is preferably a rubber-based latex, an acryl-based latex, an acrylate-based latex, or a urethane-based latex. This is because these can be dispersed in a liquid state in an uncured thermosetting resin liquid. Since both the thermosetting resin and the elastic polymer are liquid, it is easy to impregnate the porous substrate with the fibrous substrate.
  • the rubber latex is preferably nitrile-butadiene rubber (NBR) or styrene-butadiene rubber (SBR).
  • the thermosetting resin is preferably a phenol resin, a melamine resin, an epoxy resin, a polyimide resin, or the like.
  • the weight ratio of the solid content of the thermosetting resin to the elastic polymer is desirably 95/5 to 65/35.
  • the reason is that if the amount of the thermosetting resin is too large, the toughness is reduced, cracks are easily generated, the holding power of the nail is reduced, and if the amount of the elastic polymer is too large, the resin strength is reduced. However, the holding power of the nail decreases.
  • the optimal holding force of the nail is 95/5 to 65/35 in terms of the weight ratio of the solid content between the thermosetting resin and the elastic polymer.
  • the composite cured product may be used as a core material, and at least one surface thereof may have a decorative layer.
  • the decorative layer used is melamine resin paint, melamine resin impregnated paper, polyester At least one resin-based decorative layer selected from resin paint, diaryl phthalate resin impregnated paper, UV curable resin paint, vinyl chloride resin film, urethane resin paint, polyacryl urethane, fluoroplastic resin film, and decorative board , Natural wood veneer (rose
  • the decorative board has a three-layer decorative board comprising a phenolic resin-impregnated core layer, a melamine resin-impregnated pattern layer, and a melamine resin-impregnated overlay layer, a melamine resin-impregnated backing layer, a phenolic resin-impregnated core layer, and a melanin resin-impregnated layer.
  • a four-layer decorative board consisting of a pattern layer and a melamine resin-impregnated monolayer can be used.
  • the surface strength is significantly increased, and thus it can be applied to flooring and the like.
  • the thickness of this decorative layer is desirably 0.1 to 10 mm.
  • a reinforcing layer made of a resin and a fiber base is formed between the core material and the decorative layer.
  • the resin forming the reinforcing layer is preferably a thermosetting resin. This is because, 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.
  • the composite cured product of the present invention may be provided as a composite building material by attaching paper such as water-resistant paper to at least one surface.
  • the method for producing a composite cured product is as follows.
  • papermaking sludge is used as a raw material for the composite cured product.
  • Papermaking sludge includes printing paper, kraft paper, titanium paper, tissue paper, dust paper, toilet paper, sanitary products, towel paper, industrial hybrid paper, and household hybrid paper. It is desirable to use papermaking sludge discharged during papermaking.
  • Commercially available papermaking sludge can be used, for example, “Mouth ash” and “raw sludge” handled by Maruto Kiln. This papermaking sludge has a large amount of calcium compound, and it is easy to obtain Ca-based crystals by hardening.
  • This papermaking sludge is poured into a desired formwork, or into a formwork provided with a filter, and then pressed to remove moisture, or a method of papermaking sludge of papermaking sludge. Perform molding. Then, after molding, the composite cured product is obtained by drying and curing at a heating temperature of 20 to 160 ° C. 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 productivity may be reduced.
  • the papermaking sludge is conveyed by a conveyor, pressed down by a mouth into a sheet-like molded product, and the sheet-shaped molded product is heated to a heating temperature of 80 to 16 ° C. Pressing while heating at 0 ° C, forming into a plate-shaped core material.
  • An appropriate pressure at that time is l to 400 kgf / cm 2 .
  • the specific gravity can be adjusted by appropriately changing the pressure. For example, the specific gravity is approximately 1.4 at 35 O kg / cm 2 .
  • clampping refers to holding the workpiece while applying pressure.
  • the fibrous material is oriented in a direction crossing the pressing direction by the pressure applied at the time of pressing, so that the bending strength of the core material can be improved.
  • pressurization removes moisture and suppresses the progress of crystallization, which is advantageous for forming an amorphous body.
  • the inorganic powder can be dispersed in the composite cured product by adding and mixing the inorganic powder to the papermaking sludge and then heating and curing.
  • a metal alkoxide / metal hydroxide can be used as a raw material.
  • alkoxides of Al, Si, and Ca The mixture and the pulverized waste paper may be mixed, hydrolyzed and polymerized in the presence of an acid or an acid to form a sol, and the sol may be dried and cured to gel.
  • Japanese Patent Application Laid-Open No. 49-86443 discloses a hot-pressed mixture of pulp cake (cellulose component) and lime cake. It does not utilize the inorganic component in the papermaking sludge as in the present invention, nor does it disperse fibers in inorganic amorphous. For this reason, fracture at the grain boundaries of limescale or crack propagation cannot be prevented, and problems remain in bending strength and compressive strength.
  • limescale is a crystalline substance (calcium oxide) obtained by burning paper pulp liquor, and is clearly distinguished from the amorphous substance of the present invention.
  • Japanese Patent Application Laid-Open Nos. 7-4757, 7-69701, 6-9203546 and 5-2707082 each disclose cement and Japanese Patent Application Laid-Open No. H10-15923 discloses a technique in which inorganic fiber is combined with inorganic reinforcing fibers.
  • Japanese Patent Application Laid-Open No. 49-28080 discloses a technique for mixing paruvous sludge with crystalline gypsum. There is a technology that focuses only on the fibers in pulp waste, and Japanese Patent Application Laid-Open No. 53-81838 discloses that fibers (20% fiber, 0.01% sediment) and wood chips
  • Each of the techniques is described as being formed by mixing fibrous substances. However, any of the techniques is different from the one in which a fibrous substance is dispersed in an inorganic amorphous material as in the present invention.
  • Japanese Patent Application Laid-Open No. 51-30888 describes a technique for forming baked ash of pulp waste and a lightweight inorganic material, but does not describe calcination conditions and the like. Amorphous ash cannot be obtained.
  • Japanese Unexamined Patent Publication No. Hei 8—2640400 discloses a papermaking This technology uses waste paper pulp itself instead of ludge.
  • Japanese Patent Application Laid-Open No. 48-43949 discloses a technique in which pulp waste containing organic and inorganic substances is mixed with a polymer emulsion, etc., and inorganic substances include silicon oxide, aluminum oxide and aluminum oxide.
  • Iron oxide refers to substantially one type of metal oxide, and is different from two or more types of metal oxides constituting a complex amorphous system as in the present invention.
  • Japanese Patent Application Laid-Open No. 49-95952 discloses a ceramic (polycrystalline) base material, which is different from an amorphous base material as in the present invention.
  • Japanese Patent Application Laid-Open No. 55-12853 discloses a papermaking sludge made of old newspapers etc. which is wire-pressed, dewatered, dried with a dryer, and finally hot-pressed.
  • Japanese Patent Application Laid-Open No. 52-90585 discloses a cured product obtained by paraffin-coating the surface of a cured product of papermaking sludge.
  • Japanese Patent Application Laid-Open No. 50-116504 discloses cured products obtained by mixing papermaking sludge and glass fiber.
  • Japanese Patent Publication No. 57-19019 discloses a hardened paper sludge containing Si—Ai crystal.
  • the composite building material of the present invention is manufactured as follows.
  • the papermaking sludge is conveyed by a conveyor and pressed by a roll to form a sheet-like molded body.
  • the fiber base material is impregnated with a resin, and heat-treated at 25 to 0 ° C, Dry to form a reinforcing sheet.
  • the sheet-shaped molded body and the reinforcing sheet are laminated and pressed together while heating to form a composite building material comprising a core material (composite cured body) and a reinforcing layer.
  • the heating temperature here is preferably from 80 to 200 ° (: the pressure is preferably from l to 400 kgf / cm 2 .
  • the fibrous material can be oriented to increase the bending strength, and since water can be removed by applying pressure, it is possible to prevent water from being taken in and excessive crystallization.
  • the inorganic fiber mat is impregnated with the resin composition, dried and then heated and pressed, and the thermosetting resin is cured to form a reinforcing layer, and this reinforcing layer is used as an adhesive.
  • a method of sticking to a core material that has been cured in advance may be used.
  • thermosetting resin such as phenol resin is coated on the fiber surface of glass fiber, rock wool, or ceramic fiber with a different composition, and a fiber base made of these fibers is formed on a sheet-like molded body. It is also possible to adopt a method of laminating and hot pressing. This method of coating a thermosetting resin on the fiber surface in a separate process improves the adhesion to the impregnated resin, makes it easier to bond the fibers together, and further improves the impregnation rate of the luster. This is advantageous.
  • Examples of such a coating method include a method in which an uncured thermosetting resin is impregnated into the fibrous base material and dried, or a raw material melt of glass fiber, rock wool, or ceramic fiber flows out of a nozzle. Then, fiberization is performed by a blowing method or a centrifugal method, and simultaneously with the fiberization, a solution of a thermosetting resin such as a phenol resin is sprayed.
  • a thermosetting resin such as a phenol resin
  • glass fiber, mouth wool, or ceramic fiber is used as a constituent material of the fiber base material, it is preferable to coat with a silane coupling agent.
  • a silane coupling agent When glass fiber, mouth wool, or ceramic fiber is used as a constituent material of the fiber base material, it is preferable to coat with a silane coupling agent.
  • the front and back surfaces of the composite building material obtained in this way can be painted, or a decorative plate or veneer can be attached with an adhesive or the like.
  • the decorative board is composed of a core layer impregnated with fuminol resin, a melamine resin
  • a three-layer decorative board consisting of a resin-impregnated overlay layer, a melamine resin-impregnated backing layer, a fuminol resin-impregnated core layer, a melamine resin-impregnated pattern layer, and a melamine resin-impregnated overlay layer.
  • Decorative boards can be used.
  • the surface strength is significantly increased, so that it can be applied to flooring and the like.
  • high quality wood such as cedar and cypress can be used as the decorative veneer.
  • thermosetting resin for example, at least one thermosetting resin selected from phenol resin, melamine resin, epoxy resin, and urea resin is applied to the surface of the composite cured body. May be.
  • the composite cured product of the present invention may have an electromagnetic wave shielding layer formed on the surface or inside.
  • This electromagnetic wave shield layer is advantageously made of metal foil. This is because metal foil not only efficiently absorbs and absorbs electromagnetic waves, but also has high strength, light weight, and excellent workability.
  • the metal foil is at least one selected from aluminum foil, copper foil, zinc foil, stainless steel foil, gold foil, and silver foil.
  • the thickness of the metal foil is set at 10 to 500 ⁇ m.
  • the conductive shield layer may be a composite sheet made of a conductive filler and a resin. Such a sheet is advantageous because it also absorbs sound and vibration.
  • the conductive filler included in this sheet is, for example, at least one powder selected from iron, copper, aluminum, stainless steel, brass, zinc, carbon, and the like.
  • the resin is preferably at least one selected from a phenol resin, an epoxy resin, a urethane resin, a urea resin, a polyester resin, a polypropylene resin, and a polyethylene resin.
  • the thickness of the composite sheet is preferably 0.5 to 5.0 mm.
  • the conductive shield layer may be a layer coated with a conductive paint.
  • the conductive shield layer may be provided on at least one of the front surface and the back surface of the composite cured body, or may be embedded inside. Since a decorative layer is formed on the front surface, it is optimal to form the decorative layer on the back surface.
  • FIG. 1 is a schematic cross-sectional view of the composite cured product of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the composite cured product of the present invention.
  • FIG. 3 is a schematic cross-sectional view of the composite building material of the present invention.
  • FIG. 4 is an X-ray diffraction chart of Example 1.
  • FIG. 5 is an X-ray diffraction chart of Example 2.
  • FIG. 6 is a chart of X-ray diffraction of Comparative Example 1. BEST MODE FOR CARRYING OUT THE INVENTION
  • Unfired papermaking sludge (Makito Paper Co., Ltd.'s low-quality papermaking sludge “raw sludge”, solid content 51% by weight, moisture 49% by weight) was prepared by 1500 g. Next, while conveying the papermaking sludge by a conveyor, a pressure of 1 O kgf / cm 2 was applied to obtain a sheet-like molded body having a thickness of 10 mm. This sheet-shaped molded body was heated at 100 ° C. to obtain a plate-shaped composite cured body.
  • the volume can be measured by measuring the length of each side, and the specific gravity can be calculated by measuring the weight.
  • the specific gravity was 1.2.
  • the fibers were oriented in a direction perpendicular to the pressing direction.
  • Pulp 5 3 7% by weight, Mg 0: 13% by weight. / 6
  • composition of calcined sludge was measured using a fluorescent X-ray analyzer (Rigaku R1X2100). The analysis was carried out, and the results were as follows in terms of each oxide.
  • Average particle size 11.0 / m
  • a sheet-like molded body having a thickness of 10 mm was formed while applying a pressure of 5 kgf / cm 2 .
  • This sheet-shaped molded body was heated at 110 ° C. to obtain a plate-shaped composite cured body.
  • the sheet glass fiber was impregnated with a phenol resin solution containing a curing agent (impregnation amount: 45% in solid content), and then dried at a temperature of 80 ° C. for 20 minutes to obtain a reinforcing sheet. Further, a phenol resin was applied to the front and back surfaces of the core material, and dried for 8 minutes at a temperature of 8 (TC).
  • a phenol resin solution containing a curing agent impregnation amount: 45% in solid content
  • a sheet-like molded body was formed in the same manner as in Examples 1 and 2. Then, placing the reinforcing sheet on the front and back surfaces of the sheet materials, 1 1 0 ° and pressed 2 0 min at pressure 7 kgf / cm 2 at a temperature and C, 1 mm thick in both sides A composite building material consisting of a reinforcing layer and a core material having a thickness of 10 mm was manufactured. Furthermore, a 0.1 mm thick decorative cedar veneer was attached to the surface of this composite building material via a vinyl acetate adhesive.
  • the specific gravity of the core material measured in the same manner as in Examples 1 and 2 was 1.2.
  • the unsintered papermaking sludge of Examples 1 and 2 100 parts by weight of a phenol resin and 500 parts by weight of water were kneaded to obtain a kneaded product.
  • the obtained kneaded product was formed into a sheet-like molded body having a thickness of 10 mm by applying a pressure of 120 kgf / cm 2 by a dehydration press method. This sheet-shaped molded body was heated at 110 ° C. to obtain a plate-shaped composite cured body.
  • the kneaded material is pressed by a dewatering press method at a pressure of 65 kgf / cm 2 while a sheet having a thickness of 10 mm is pressed. G-shaped molding. This sheet-shaped molded body was heated at 110 ° C. to obtain a plate-shaped composite cured body.
  • a 10 mm-thick sheet-shaped molded body While applying a pressure of 1 70 kgf / cm 2 (16.7 MPa), a 10 mm-thick sheet-shaped molded body is heated and dried at 10 o ° c to form a composite. It was a cured body. Further, an aluminum foil (thickness: 100 m) was adhered to one surface of the composite cured product with a vinyl acetate adhesive.
  • a paper impregnated paper impregnated with melamine resin on a titanium paper (ash content 8% by weight) printed with a grain pattern was laminated on the composite surface of Examples 1 and 2, and a pressure of 150 kg: 40 kg / cm 2 was applied. Formed a decorative layer on the surface.
  • Pulp 76.0% by weight, Mg 0: 0.1% by weight
  • Example 2 To the papermaking sludge of Example 1, a 10% ethyl alcohol solution of calcium ethoxide was added and stirred to prepare an excess of papermaking sludge of Ca.
  • the cured composites and composite building materials obtained in the above Examples and Comparative Examples were tested for bending strength, compressive strength, workability, and nailing properties.
  • the results are shown in Table 1.
  • the test method was measured according to the flexural strength specified by JISA 6901, and the compressive strength was measured according to the method specified by JISA 5416.
  • the workability was determined by cutting with a woodworking circular saw. Furthermore, regarding nailing properties, nails with a diameter of 4 mm and a length of 50 mm were hit and checked for cracks. Beta.
  • the fracture toughness value was calculated from the length of the cracks generated by injecting an indenter using a Pikkas hardness meter (MVK-D, Akashi Seisakusho).
  • the Young's modulus was 1.4 to 2.7 ⁇ 10 4 kgf / cm 2 , and the toughness value was calculated using these values.
  • Example 1 the upper row corresponds to Example 1 and the lower row corresponds to Example 2.
  • the crystal structure was confirmed by X-ray diffraction.
  • the X-ray diffraction charts are shown in FIGS. 4 and 5, respectively.
  • Rigaku MiniFlex was used, and Cu was set as an evening getter.
  • Example 3 the same papermaking sludge as that used in Examples 1 and 1 was used in the same manner as those Examples.
  • the amorphous structure has a structure in which the crystal structure of calcium carbonate, which is an inorganic crystal containing Ca, is mixed.
  • the composite cured product of the present invention is excellent in workability and productivity, has high bending strength and compressive strength, and is made of inexpensive material because of using industrial waste.
  • Advantageous applications in various fields are possible, and in particular, the ability to drive nails makes it possible to provide the best materials for building materials at low cost. Also, it has high fracture toughness and can be used for various applications.

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Abstract

Cet article composite durci est caractérisé en ce qu'il comprend un article minéral amorphe dans lequel sont incorporés des cristaux minéraux contenant Ca ainsi que des morceaux d'une substance fibreuse. On peut utiliser cet article composite durci pour améliorer la résistance à la flexion d'un article composite sans nuire aux propriétés de traitement ou de rendement de celui-ci.
PCT/JP2000/003788 1999-12-10 2000-06-09 Article composite durci et materiau de construction composite WO2001042565A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JPPCT/JP/99/6970 1999-12-10
PCT/JP1999/006970 WO2000036242A1 (fr) 1998-12-11 1999-12-10 Materiau de construction composite
JPPCT/JP/99/6969 1999-12-10
PCT/JP1999/006968 WO2000036218A1 (fr) 1998-12-11 1999-12-10 Materiau composite durci et procede de fabrication correspondant, materiaux de construction en feuilles a base de ce materiau composite durci, et materiaux de construction composites
PCT/JP1999/006969 WO2000035820A1 (fr) 1998-12-11 1999-12-10 Poudre non cristalline, produit durci composite et materiau de construction composite
JPPCT/JP/99/6968 1999-12-10

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50101604A (fr) * 1974-01-18 1975-08-12
JPS5212227A (en) * 1975-07-21 1977-01-29 Noda Plywood Mfg Co Ltd Glass fibre boards and method of production thereof
JPS5290585A (en) * 1976-01-23 1977-07-29 Miura Seisakusho Kk Process for manufacturing waterrresistant object composed of paper sludge and paraffin
JPS5512853A (en) * 1978-07-10 1980-01-29 Heisaku Inagawa Production of board using paper making sludge
JPS5719019B2 (fr) * 1977-06-18 1982-04-20
JPS58176159A (ja) * 1982-04-07 1983-10-15 日本セメント株式会社 非晶質ケイ酸カルシウム成形体の製造方法
JPH0497924A (ja) * 1990-08-15 1992-03-30 Takenaka Komuten Co Ltd 補強材入板ガラス
US5350716A (en) * 1984-08-09 1994-09-27 Corning Incorporated Fiber-reinforced composites
JPH0710633A (ja) * 1993-06-18 1995-01-13 Sekisui Chem Co Ltd 無機質硬化体の製造方法
JPH0757748A (ja) * 1993-07-23 1995-03-03 Mitsubishi Heavy Ind Ltd 高温用ガスケット材とその製造法
JPH0920532A (ja) * 1995-07-03 1997-01-21 Ube Ind Ltd 高強度高靱性ガラス複合材料及びガラス複合粉末並びにそれらの製造方法
JPH10109305A (ja) * 1996-10-08 1998-04-28 Mitsui Petrochem Ind Ltd 石膏ボードの製造方法
JPH11315593A (ja) * 1998-02-19 1999-11-16 Ibiden Co Ltd 耐火性複合建築材料および耐火性複合床材

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50101604A (fr) * 1974-01-18 1975-08-12
JPS5212227A (en) * 1975-07-21 1977-01-29 Noda Plywood Mfg Co Ltd Glass fibre boards and method of production thereof
JPS5290585A (en) * 1976-01-23 1977-07-29 Miura Seisakusho Kk Process for manufacturing waterrresistant object composed of paper sludge and paraffin
JPS5719019B2 (fr) * 1977-06-18 1982-04-20
JPS5512853A (en) * 1978-07-10 1980-01-29 Heisaku Inagawa Production of board using paper making sludge
JPS58176159A (ja) * 1982-04-07 1983-10-15 日本セメント株式会社 非晶質ケイ酸カルシウム成形体の製造方法
US5350716A (en) * 1984-08-09 1994-09-27 Corning Incorporated Fiber-reinforced composites
JPH0497924A (ja) * 1990-08-15 1992-03-30 Takenaka Komuten Co Ltd 補強材入板ガラス
JPH0710633A (ja) * 1993-06-18 1995-01-13 Sekisui Chem Co Ltd 無機質硬化体の製造方法
JPH0757748A (ja) * 1993-07-23 1995-03-03 Mitsubishi Heavy Ind Ltd 高温用ガスケット材とその製造法
JPH0920532A (ja) * 1995-07-03 1997-01-21 Ube Ind Ltd 高強度高靱性ガラス複合材料及びガラス複合粉末並びにそれらの製造方法
JPH10109305A (ja) * 1996-10-08 1998-04-28 Mitsui Petrochem Ind Ltd 石膏ボードの製造方法
JPH11315593A (ja) * 1998-02-19 1999-11-16 Ibiden Co Ltd 耐火性複合建築材料および耐火性複合床材

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