WO2022004640A1 - 積層成形板およびその製造方法 - Google Patents
積層成形板およびその製造方法 Download PDFInfo
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- WO2022004640A1 WO2022004640A1 PCT/JP2021/024320 JP2021024320W WO2022004640A1 WO 2022004640 A1 WO2022004640 A1 WO 2022004640A1 JP 2021024320 W JP2021024320 W JP 2021024320W WO 2022004640 A1 WO2022004640 A1 WO 2022004640A1
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- Prior art keywords
- mass
- fiber
- molded plate
- laminated molded
- less
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Links
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 35
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
- B28B1/40—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon by wrapping, e.g. winding
- B28B1/42—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon by wrapping, e.g. winding using mixtures containing fibres, e.g. for making sheets by slitting the wound layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/52—Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement
- B28B1/527—Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement by delivering the materials on a rotating drum, e.g. a sieve drum, from which the materials are picked up by a felt
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/02—Cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0641—Polyvinylalcohols; Polyvinylacetates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a laminated molded plate and a method for manufacturing the same.
- cement-based papermaking boards are obtained by molding a sheet by a papermaking method in which a slurry in which cement and fibers are suspended in an aqueous medium is made with a mesh, and then cured by curing.
- the abstraction method is widely used in a wide range of fields due to its versatility in manufacturing, especially in the construction field, for ceiling materials, interior materials, exterior materials, floor materials, and the like.
- the production of cement requires a great deal of energy, and the associated emission of a large amount of carbon dioxide is regarded as a problem. Therefore, in recent years, an inorganic polymer produced by reacting an aluminosilicate with an alkali metal silicate has been studied. Compared to cement-based materials, such inorganic polymers are superior in durability and acid resistance, and emit much less carbon dioxide from the manufacture of raw materials to the manufacture of products, and are therefore attracting attention as environmentally friendly materials. It's coming.
- blast furnace slag is 30 to 53% by mass
- plaster having an average particle size of 200 to 2000 ⁇ m is 2 to 5% by mass
- alkaline material is 5 to 11% by mass
- reinforcing fibers are based on the total solid content. 5 to 15% by mass, and 31 to 50% by mass of the inorganic admixture
- the mass ratio of blast furnace slag: gypsum: alkaline material is 1: 0.05 to 0.15: 0.15 to 0.35.
- Described is an inorganic plate characterized by being a cured product of a mat formed by dehydrating the slurry.
- polyvinyl alcohol fiber having a cross-sectional solidity of 40 to 70% is 1.0 to 2.0% by mass in the total solid content, and eucalyptus pulp having a drainage degree of 100 to 500 ml is contained in the total solid content.
- Patent Document 1 contains blast furnace slag as an environmentally friendly raw material, but since the amount of blast furnace slag is small, the bending strength is low, and further improvement in dimensional stability is required.
- Patent Document 3 is formed from a curable composition containing (A) at least one aluminosilicate source, (B) alkali metal hydroxide, (C) calcium ion source and (D) alkali resistant fibers. A molded body in which the aluminosilicate source (A) contains a specific aluminosilicate source is described.
- This molded body is a molded body manufactured by a molding method such as a casting method, a dehydration molding method, an injection molding method, or an extrusion molding method, and in the same document, a manufacturing plate manufactured by a manufacturing method is targeted. Not. In view of the above circumstances, it is an object of the present invention to provide a laminated molded plate reinforced with fibers and having high bending strength, high impact strength and high dimensional stability.
- the present inventors have completed the present invention as a result of diligent studies on the laminated molded plate in order to solve the above-mentioned problems. That is, the present invention includes the following preferred embodiments.
- [1] Formed from a curable composition comprising (A) an aluminosilicate source, (B) an alkaline metal hydroxide, (C) a cellulose-based fiber and (D) an alkali-resistant fiber other than the cellulose-based fiber.
- the molded plate a laminated molding plate comprising two or more that includes the aluminosilicate source (a) blast furnace slag, the specific surface area of the blast furnace slag is 1000 cm 2 / g or more, or less 9000 cm 2 / g blast furnace
- the aluminosilicate source (A) contains at least one selected from the group consisting of fly ash, metakaolin and red mud in an amount of 1% by mass or more and 35% by mass based on the total solid content of the curable composition.
- [6] The laminated molded plate according to any one of [1] to [5] above, wherein the alkaline metal hydroxide (B) is slaked lime.
- the cellulosic fiber (C) is pulp.
- the alkali-resistant fiber (D) other than the cellulose-based fiber is at least one selected from the group consisting of polyvinyl alcohol-based fiber, polyethylene fiber, polypropylene fiber, acrylic fiber, aramid fiber and nylon fiber. 1] The laminated molded plate according to any one of [8].
- the laminated molded plate of the present invention is curable and contains (A) an aluminosilicate source, (B) an alkaline metal hydroxide, (C) a cellulosic fiber and (D) an alkali-resistant fiber other than the cellulosic fiber. It is a laminated molded plate including two or more molded plates formed from the composition. It includes aluminosilicate source (A) blast furnace slag, the specific surface area of 1000 cm 2 / g or more, the content of the blast furnace slag is not more than 9000 cm 2 / g is 55% by weight based on the total solids of the curable composition It exceeds 90% by mass and is 90% by mass or less.
- A aluminosilicate source
- blast furnace slag the specific surface area of 1000 cm 2 / g or more, the content of the blast furnace slag is not more than 9000 cm 2 / g is 55% by weight based on the total solids of the curable composition It exceeds 90%
- the aluminosilicate source contains aluminosilicate (xM 2 O, yAl 2 O 3 , zSiO 2 , nH 2 O, M is an alkali metal) as a main component.
- the main component means the component having the largest mass in the aluminosilicate source.
- the aluminosilicate source elutes cations such as aluminum and silicon by contact with a highly alkaline solution [an aqueous solution of an alkaline metal hydroxide (B)], and these are polycondensed to form a strong SiO 4 -A polymer network of AlO 4 is formed.
- the aluminosilicate source (A) used in the present invention contains blast furnace slag. Therefore, according to the present invention, the blast furnace slag, which is a waste generated in the steelmaking process, is effectively utilized.
- a laminated molded plate containing two or more molded plates formed from a curable composition containing the components (A) to (D) has a thickness of 1000 cm.
- Laminated molded plate when the content of blast furnace slag having a specific surface area of 2 / g or more and 9000 cm 2 / g or less exceeds 55% by mass and 90% by mass or less with respect to the total solid content of the curable composition.
- the content is 55% by mass or less, it is difficult for the laminated molded plate to have the desired bending strength, impact strength and dimensional stability.
- the laminated molded plate when the content is higher than 90% by mass, it is difficult for the laminated molded plate to have the desired bending strength, impact strength and dimensional stability. It is considered that this is because the optimum blending ratio of the alkaline metal hydroxide (B), the cellulosic fiber (C) and the alkaline resistant fiber (D) cannot be obtained due to the content being too high.
- the above is an estimation, and the present invention is not limited to these mechanisms of action.
- the curable composition contains more than 55% by mass of the blast furnace slag having a specific surface area of less than 1000 cm 2 / g with respect to the total solid content of the curable composition, the desired bending strength, impact strength and It is difficult to obtain a laminated molded plate having a dimensional change rate. Further, even if the curable composition contains 60% by mass or more of the blast furnace slag having a specific surface area of more than 9000 cm 2 / g with respect to the total solid content of the curable composition, the desired bending strength, impact strength and dimensional change are obtained. It is difficult to obtain a laminated molded plate with a specific surface area.
- the content of the blast furnace slag having a specific specific surface area is preferably 60% by mass or more, more preferably 62% by mass or more, further preferably 65% by mass or more, particularly preferably 68% by mass or more, and preferably 85% by mass. It is mass% or less, more preferably 82% by mass or less, still more preferably 80% by mass or less, and particularly preferably 75% by mass or less.
- blast furnace slag having sufficient reaction sites in the produced solid content is sufficient.
- the optimum blending ratio of the alkaline metal hydroxide (B), the cellulosic fiber (C) and the alkali-resistant fiber (D) was obtained, and as a result, more in the manufactured laminated molded plate. High bending strength, higher impact strength and higher dimensional stability are likely to be obtained.
- the specific surface area of the blast furnace slag contained in a content of more than 55% by mass and 90% by mass or less with respect to the total solid content of the curable composition is preferably 2000 cm 2 / g or more, more preferably 3000 cm 2 / g or more. It is preferably 8000 cm 2 / g or less, and more preferably 7000 cm 2 / g or less.
- the specific surface area of the blast furnace slag is not less than the lower limit value and not more than the upper limit value, the blast furnace slag tends to have a sufficient reaction site and a suitable average particle size, and as a result, in the manufactured laminated molded plate. , Higher bending strength, higher impact strength and higher dimensional stability are likely to be obtained.
- the specific surface area of the blast furnace slag can be adjusted to be equal to or higher than the lower limit value and lower than the upper limit value by, for example, pulverizing and classifying the blast furnace slag and using a specific fraction.
- the specific surface area of the blast furnace slag can be measured by, for example, a laser diffraction / scattering method.
- Blast furnace slag is commercially available, 1000 cm 2 / g or more, may be used alone or in combination of commercially available products having the specific surface area of 9000 cm 2 / g, or more.
- blast furnace slag There are two types of blast furnace slag: slow cooling slag, which is crystalline, and granulated slag, which is amorphous, both of which can be used in the present invention. It is preferable to use granulated slag from the viewpoint that it is easy to further improve the strength or promote the curing of the laminated molded plate.
- aluminosilicate sources (A) other than blast furnace slag with a particular specific surface area are industrial wastes such as fly ash, red mud, and sewage sludge incineration ash; natural aluminosilicate minerals and their calcined products. (For example, metakaolin), as well as volcanic ash and the like can be mentioned. These substances are commercially available, and in the present invention, they may be used alone or in combination of two or more. Further, as long as they do not impair the effects of the present invention, the curable composition of the present invention has a specific surface area of blast furnace slag and / or the specific surface area of less than 1000 cm 2 / g may comprise blast furnace slag 9000 cm 2 / g greater.
- the aluminosilicate source (A) has a curable composition of at least one selected from the group consisting of fly ash, metakaolin and red mud, in addition to blast furnace slag having a specific specific surface area. It is further contained in a content of preferably 1% by mass or more, preferably 35% by mass or less with respect to the total solid content of the product.
- the compaction of the cured product is likely to be increased as compared with the case where the blast furnace slag is used alone as the aluminosilicate source (A), it has higher bending strength, higher impact strength and higher dimensional stability. It is easy to obtain a laminated molded plate.
- the content is more preferably 3% by mass or more, further preferably 4% by mass or more, still more preferably 5% by mass or more, particularly preferably 6% by mass or more, still more preferably 34% by mass.
- the content is preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 12% by mass or less, and particularly preferably 10% by mass or less.
- fly ash is contained as the alminosilicate source (A)
- the content of fly ash is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably, based on the total solid content of the curable composition. Is 4% by mass or more, preferably 25% by mass or less, more preferably 23% by mass or less, still more preferably 21% by mass or less, still more preferably 15% by mass or less, particularly preferably 13% by mass or less, and particularly more. It is preferably 12% by mass or less.
- the content of fly ash may be 5% by mass or more, 6% by mass or more, 8% by mass or more, and 7% by mass or less. , 6% by mass or less.
- red mud is contained as the silicate source (A) of aluminum
- the content of red mud is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total solid content of the curable composition. It is more preferably 4% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass or more, particularly preferably 9% by mass or more, still more preferably 11% by mass or more, and preferably 35% by mass. Below, it is more preferably 33% by mass or less, further preferably 30% by mass or less, still more preferably 28% by mass or less, particularly preferably 25% by mass or less, and particularly more preferably 20% by mass or less.
- the content of red mud may be 15% by mass or more, 20% by mass or more, while 15% by mass or less, or 10% by mass or less. However, it may be 8% by mass or less, or 6% by mass or less.
- the content of the blast furnace slag having a specific specific surface area is preferably 56% by mass or more, more preferably 57% by mass or more, still more preferably 58% by mass or more, and further more than the total solid content of the curable composition. It is preferably 60% by mass or more, particularly preferably 62% by mass or more (in one embodiment, for example, 64% by mass or more, preferably 67% by mass or more, more preferably 70% by mass or more), and preferably 87% by mass or less.
- the content is not less than the lower limit value and not more than the upper limit value, it is easy to obtain the effect of adding at least one selected from the group consisting of fly ash, metakaolin and red mud described above.
- the alkaline metal hydroxide (B) used in the present invention exhibits high alkalinity in water, and when it comes into contact with the aluminosilicate source (A), it activates it and elutes cations such as Al and Si. Has the effect of causing.
- alkaline metal hydroxide (B) examples include slaked lime, quicklime and sodium hydroxide. It is preferable to use slaked lime as the alkaline metal hydroxide (B) from the viewpoint of easily avoiding the problem that the metal hydroxide flows out or is diluted in the circulating water of the process in the papermaking method.
- the content of the alkaline metal hydroxide (B) is preferably 3% by mass or more, more preferably 4% by mass or more, still more preferably 6% by mass or more, based on the total solid content of the curable composition. More preferably, it is 7% by mass or more, particularly preferably 8% by mass or more, more preferably 45% by mass or less, still more preferably 43% by mass or less, and particularly preferably 41% by mass or less. Further, in a preferred embodiment, the content is preferably 10% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 22% by mass or less, and particularly preferably 20% by mass. It is as follows. When the content is not less than the lower limit value and not more than the upper limit value, higher bending strength, higher impact strength and higher dimensional stability are likely to be obtained in the manufactured laminated molded plate.
- the cellulosic fiber (C) used in the present invention has an effect of increasing the bending strength and impact strength of the laminated molded plate.
- the cellulose-based fiber (C) examples include rayon fiber (including polynosic rayon fiber and organic solvent-based cellulose fiber), acetate-based fiber, and natural pulp (wood pulp, cotton linter pulp, linen, pulp, etc.). Examples include cellulose-based fibers. Among these, it is preferable to use natural pulp, and more preferably to use pulp, from the viewpoint of easily increasing the yield rate in the circular net process at the time of papermaking in the papermaking method. Therefore, in a preferred embodiment of the present invention, the cellulosic fiber (C) is pulp.
- the pulp may be beaten or not beaten. From the viewpoint of easily obtaining the desired bending strength and impact strength, it is preferable to use the beat-treated pulp, and the beating degree measured according to the Canadian standard type of the drainage test method JIS P8121-1976 is the CSF value. It is more preferable to use pulp which is 50 to 400 mL, more preferably 100 to 150 mL.
- pulp can be used as pulp.
- pulp include conifers, hardwoods, Manila hemp, mitsumata, mulberry, ganpi, sarago, mulberry, straw, bamboo, reed, sabai, laran grass, esparto, bagasse, sisal, kenaf, linter, banana and waste paper.
- Coniferous trees include coniferous trees such as Sugi family, Matsu family, Cercidiphyllaceae, and Araucariaceae
- examples of the broad-leaved trees include Nire family, Beech family, Futomomo family, Cercidiphyllaceae, Mokusei family, and Mikan.
- Broad-leaved trees such as Family, Cercidiphyllaceae, Cercidiphyllaceae, Walnut, Araucariaceae, Araucariaceae, Araucariaceae, Cercidiphyllaceae, Cercidiphyllaceae, Moctenaceae, Aogiriaceae and the like can be mentioned.
- These pulps may be bleached pulp or unbleached pulp. The pulp may be used alone or in combination of two or more.
- the content of the cellulosic fiber (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and particularly preferably 2% by mass or more, based on the total solid content of the laminated molded plate. It is 3% by mass or more, more preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 9% by mass or less, and particularly preferably 5% by mass or less.
- the content is equal to or higher than the lower limit, for example, when the laminated molded plate is manufactured by the manufacturing method, the blast furnace slag is easily captured by the papermaking net, and it is easy to achieve a good yield rate, and at the same time, the blast furnace slag is finished.
- the solid content is likely to contain blast furnace slag having a sufficient content, and it is easy to obtain desired bending strength and impact strength in the laminated molded plate. Further, when the content is not more than the upper limit, problems such as a decrease in water resistance of the laminated molded plate or a decrease in the invasion suppressing effect of corrosive substances (various organic acids such as chlorine, carbon dioxide, and sulfate ion) are avoided. Easy to get rid of.
- the alkali-resistant fiber (D) other than the cellulosic fiber used in the present invention has an effect of increasing the bending strength and impact strength of the laminated molded plate.
- the cellulosic fiber (C) and the alkali-resistant fiber (D) other than the cellulosic fiber (hereinafter, may be abbreviated as "alkali-resistant fiber (D)") in combination the reinforcing effect of the fiber can be enhanced. It was found that it could be improved synergistically.
- the alkali-resistant fiber (D) may be an inorganic fiber or an organic fiber as long as it has chemical durability against alkali.
- alkali-resistant inorganic fibers include alkali-resistant glass fibers and carbon fibers.
- alkali-resistant organic fibers include polyvinyl alcohol (hereinafter, may be referred to as PVA) fiber, polyolefin fiber (for example, polyethylene fiber and polypropylene fiber, etc.), ultrahigh molecular weight polyethylene fiber, and polyamide fiber (polyamide 6).
- Polyamides 6, 6, and polyamides 6, 10, etc. include aramid fibers (particularly para-aramid fibers), polyparaphenylene benzobisoxazole-based fibers [eg, polyparaphenylene benzoxazole (PBO) fibers], nylon fibers, acrylic fibers, polyphenylene.
- PPS fiber polyparaphenylene benzoxazole
- PEEK fiber polyether ether ketone fiber
- the alkali-resistant fiber (D) other than the cellulose-based fiber is selected from the group consisting of polyvinyl alcohol-based fiber, polyethylene fiber, polypropylene fiber, acrylic fiber, aramid fiber and nylon fiber at least. It is preferably one.
- the average fiber diameter of the alkali-resistant fiber (D) is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 50 ⁇ m or less, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 7 ⁇ m or more.
- the average fiber diameter of the alkali-resistant fiber (D) is not more than the upper limit value, such an alkali-resistant fiber has sufficient fiber strength and is easily industrially stably produced.
- the average fiber diameter of the alkali-resistant fibers (D) is at least the above lower limit value, the fibers are more likely to be dispersed more uniformly in the polymer matrix.
- the polymer matrix hereinafter, also referred to as “matrix”) means a polymer portion to which alkali-resistant fibers are bonded in a laminated molded plate.
- the aspect ratio of the alkali-resistant fiber (D) is preferably 50 from the viewpoint that it is easy to achieve both good dispersibility of the fiber in the curable composition and good reinforcing property after curing of the curable composition.
- the above is more preferably 150 or more, further preferably 200 or more, preferably 2000 or less, more preferably 1200 or less, still more preferably 800 or less.
- the aspect ratio means the ratio (L / D) of the average fiber length L and the average fiber diameter D.
- the average fiber diameter and aspect ratio of the alkali-resistant fiber (D) can be determined in accordance with JIS L 1015 "Chemical Fiber Staple Test Method (8.5.1)".
- the average fiber length of the alkali-resistant fiber (D) is preferably 0. From the viewpoint of easily achieving both good dispersibility of the fiber in the curable composition and good reinforcing property after curing of the curable composition. It is 5 to 20 mm, more preferably 1 to 15 mm.
- the fiber tensile strength of the alkali-resistant fiber (D) in the present invention is preferably 3 cN / dtex or more, more preferably 5 cN / dtex or more, and particularly preferably 7 cN / dtex or more.
- the upper limit of the fiber tensile strength of the alkali-resistant fiber (D) in the present invention is appropriately set according to the type of fiber, and is, for example, 30 cN / dtex or less.
- the fiber tensile strength can be obtained in accordance with JIS L 1015 "Chemical fiber staple test method (8.5.1)".
- a PVA-based fiber for example, a vinylon fiber
- the alkali-resistant fiber (D) a PVA-based fiber having the following characteristics may be used.
- the degree of polymerization of the PVA-based polymer constituting the PVA-based fiber can be appropriately selected depending on the intended purpose, and is not particularly limited. Considering the mechanical properties of the obtained fiber and the like, the average degree of polymerization of the PVA-based polymer determined from the viscosity of the aqueous solution at 30 ° C. is preferably about 500 to 20000, more preferably about 800 to 15000, and particularly preferably about 1000 to. It is about 10,000.
- the average degree of polymerization of the PVA-based polymer is preferably 1000 or more, more preferably 1200 or more, more preferably 1500 or more, and particularly preferably 1750 or more.
- the PVA-based polymer may be a medium-polymerization product having an average degree of polymerization of 1000 or more and less than 3000, or a high-polymerization product having an average degree of polymerization of 3000 or more.
- the degree of saponification of the PVA-based polymer can also be appropriately selected according to the purpose and is not particularly limited.
- the saponification degree of the PVA-based polymer may be, for example, 95 mol% or more, preferably 98 mol% or more.
- the saponification degree of the PVA-based polymer may be 99 mol% or more, or may be 99.8 mol% or more.
- the PVA-based fiber used in the present invention is produced by dissolving such a PVA-based polymer in a solvent, spinning it by either a wet method, a dry wet method, or a dry method, and drying and heat-stretching it.
- Wet spinning is a method of discharging a spinning stock solution directly from a spinning nozzle into a solidification bath.
- Dry-wet spinning is a method in which a spinning stock solution is once discharged from a spinning nozzle into air at an arbitrary distance or into an inert gas, and then introduced into a solidification bath.
- Dry spinning is a method of discharging a spinning stock solution into the air or an inert gas.
- the PVA-based fiber may be drawn if necessary.
- acetalization treatment or the like which is generally performed for PVA-based fibers, may be performed.
- the solvent used for the spinning stock solution of PVA-based fibers is not particularly limited as long as it is a solvent capable of dissolving PVA.
- a solvent capable of dissolving PVA for example, one or a combination of two or more such as water, dimethyl sulfoxide (DMSO), dimethylformamide, dimethylacetamide and polyhydric alcohols (eg, glycerin, ethylene glycol and triethylene glycol) may be used.
- DMSO dimethyl sulfoxide
- dimethylformamide dimethylacetamide
- polyhydric alcohols eg, glycerin, ethylene glycol and triethylene glycol
- water or an organic solvent as the solvent.
- water and DMSO are particularly preferable from the viewpoint of ease of supply and the influence on the environmental load.
- the polymer concentration in the spinning stock solution varies depending on the composition and degree of polymerization of the PVA-based polymer and the type of solvent, but is generally 6 to 60% by mass.
- the above solvent may be used even in dry spinning.
- water may be used or an organic solvent may be used.
- the undiluted spinning solution may contain additives and the like, depending on the purpose, in addition to the PVA-based polymer.
- additives include boric acid, surfactants, antioxidants, decomposition inhibitors, antifreeze agents, pH regulators, concealing agents, colorants, oils and the like.
- the solvent used in the solidification bath may be appropriately selected depending on the type of solvent used in the spinning stock solution.
- the undiluted spinning solution is an aqueous solution
- an aqueous solution of inorganic salts having a solidifying ability with respect to the PVA-based polymer for example, sodium sulfate, ammonium sulfate, sodium carbonate, sodium hydroxide, etc.
- an alkaline aqueous solution may be used as the solidification bath.
- the solidification bath has the ability to solidify PVA-based polymers such as alcohols such as methanol, ethanol, propanol or butanol, and ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
- PVA-based polymers such as alcohols such as methanol, ethanol, propanol or butanol, and ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
- An organic solvent having the above may be used.
- PVA-based fibers obtained by dry spinning or PVA-based fibers obtained by wet spinning from a spinning stock solution using water or an organic solvent as a solvent are preferable from the viewpoint of fiber tensile strength.
- the raw yarn may be passed through an extraction bath, or the raw yarn may be wet-stretched at the same time as extraction. Further, after wet stretching, the fibers may be dried, and if necessary, further dry heat stretching may be performed.
- the total stretching ratio (the product of the wet stretching and the stretching ratio after drying) may be, for example, 5 to 25 times, preferably about 8 to 20 times.
- the alkali-resistant fiber (D) may be used as the alkali-resistant fiber (D), and examples thereof include organic fibers such as polyvinyl alcohol fiber manufactured by Kuraray Co., Ltd., polypropylene fiber manufactured by Daiwa Spinning Co., Ltd., and nylon fiber manufactured by Toray Co., Ltd. , And inorganic fibers such as glass fibers manufactured by Nippon Denki Glass Co., Ltd. and Pacific Material Co., Ltd.
- organic fibers such as polyvinyl alcohol fiber manufactured by Kuraray Co., Ltd., polypropylene fiber manufactured by Daiwa Spinning Co., Ltd., and nylon fiber manufactured by Toray Co., Ltd.
- inorganic fibers such as glass fibers manufactured by Nippon Denki Glass Co., Ltd. and Pacific Material Co., Ltd.
- the content of the alkali resistant fiber (D) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably, with respect to the total solid content of the laminated molded plate. Is 0.3% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
- the content of the alkali-resistant fiber (D) in the laminated molded plate can be measured by the following procedure.
- the laminated molded plate is dried at 105 ° C. until it reaches a constant weight, and then weighed (W 1 (g)).
- W 1 (g) the laminated molded plate is crushed in a mortar, water is added to the crushed product, and the mashed product is filtered through a wire mesh (for example, a 55-mesh wire mesh) to obtain the alkali-resistant fiber (D), the cellulosic fiber (C), and the matrix.
- a wire mesh for example, a 55-mesh wire mesh
- the laminated molded plate in the present invention may further contain a powder other than the aluminosilicate source (A) as the other powder (E).
- a powder other than the aluminosilicate source (A) as the other powder (E).
- other powders (E) include silica fume, calcium carbonate, bentonite, and calcium sulfate derivatives (eg, dihydrate gypsum, drainage gypsum, ⁇ - or ⁇ -type hemihydrate gypsum, and anhydrous gypsum). These can be mentioned, and these may be used alone or in combination of two or more. It is preferable that the laminated molded plate contains silica fume because better dimensional stability is likely to be achieved in the laminated molded plate.
- the content thereof is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total solid content of the laminated molded plate. More preferably 2% by mass or more, particularly preferably 3% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. be.
- the content is not less than the lower limit value and not more than the upper limit value, the effect of adding the other powder (E) described above can be easily obtained.
- the cured product in the present invention may further contain a slag stimulant (F).
- a slag stimulant (F) When the slag stimulant (F) is added to the curable composition in the present invention, it is easy to obtain a cured product having higher bending strength.
- the slag stimulant (F) include aluminum sulfate, calcium hydroxide, sodium sulfate, sodium aluminate and the like, and these may be used alone or in combination of two or more.
- the cured product contains at least one selected from the group consisting of aluminum sulfate, calcium hydroxide and sodium aluminate.
- the content thereof is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the cured product. It is more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, preferably 6% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less.
- the content is not less than the lower limit value and not more than the upper limit value, the effect of adding the above-mentioned slag stimulant (F) can be easily obtained.
- the thickness of the laminated molded plate can be appropriately selected depending on the application, but is usually 4 mm or more and 30 mm or less.
- the thickness of the laminated molded plate is preferably 4 mm or more and 20 mm or less, and when used as a floor material, the thickness of the laminated molded plate is 8 mm or more and 30 mm or less. It is preferable to have.
- the thickness of the laminated molded plate can be measured by the method described in Examples described later.
- the bulk specific gravity of the laminated molded plate can be appropriately selected depending on the intended use, but is usually 0.5 g / cm 3 or more and 2.0 g / cm 3 or less.
- the bulk specific gravity of the laminated molded plate is preferably 0.8 g / cm 3 or more, more preferably 1.0 g / cm 3 or more, preferably 1.8 g / cm 3 or less, and more preferably 1.6 g / cm 3. It is as follows.
- the bulk specific gravity of the laminated molded plate can be measured by the method described in Examples described later.
- Impact strength is measured according to JIS K 7111 of the laminated molding plate is preferably 2 kJ / m 2 or more, more preferably 2.5 kJ / m 2 or more, still more preferably 3 kJ / m 2 or more.
- the upper limit of the impact strength is not particularly limited.
- the impact strength is usually 7 kJ / m 2 or less. When the impact strength is equal to or higher than the above lower limit, it is easy to prevent damage due to impact when the laminated molded plate is used as a wall material, and it is possible to prevent damage due to falling objects when the laminated molded plate is used as a floor material. Cheap.
- the bending strength measured according to JIS A 1408 of the laminated molded plate is preferably 10 N / mm 2 or more, more preferably 11 N / mm 2 or more, more preferably 12 N / mm 2 or more, still more preferably 13 N / mm. 2 or more, particularly preferably 17 N / mm 2 or more.
- the upper limit of the bending strength is not particularly limited.
- the bending strength is usually 35 N / mm 2 or less.
- the laminated molded plate of the present invention is preferably manufactured by a papermaking method.
- the papermaking method is a slurry-like curable composition in which a solid component such as aluminosilicate and a fibrous component such as a cellulosic fiber (C) and an alkali-resistant fiber (D) are turbid in an aqueous medium on a mesh. It is a method of forming a solid content that has been made into a slurry.
- Examples of the papermaking method include a circular net method or a long net method in which thin plate-shaped solids are sequentially laminated to obtain a laminated molded plate having a desired thickness, and once or more using a thick curable composition.
- a flow-on method that secures a certain thickness by making several times can be mentioned.
- the laminated molded plate can be mass-produced mechanically and continuously in a batch manner, and the manufactured laminated molded plate can have uniform and stable performance.
- a relatively thin plate of about 2 to 30 mm can be manufactured. The production of such a relatively thin plate is extremely difficult by a production method other than the papermaking method (for example, a casting method).
- the laminated molded plate of the present invention is, for example, A step of mixing an aluminosilicate source (A), an alkaline metal hydroxide (B), a cellulosic fiber (C), an alkali-resistant fiber (D) other than the cellulosic fiber, and water to prepare a curable composition.
- It can be produced by a method including a step of obtaining a molded plate by a papermaking method using the obtained curable composition and a step of laminating two or more obtained molded plates.
- these optional components are aluminosilicate source (A), alkaline metal hydroxide (B), cellulose.
- Alkaline-resistant fibers (D) other than the system fibers (C) and the cellulosic fibers can be added in the first mixing step of mixing with water.
- Examples of the other powder (E) and slag stimulant (F) include ⁇ (A) aluminosilicate source>, ⁇ (B) alkaline metal hydroxide>, ⁇ (C) cellulose-based fiber>, and so on. Those described in the paragraphs ⁇ (D) Alkaline-resistant fibers other than cellulose-based fibers>, ⁇ (E) Other powders> and ⁇ (F) Slag stimulants> can be used, respectively.
- the preparation method in the step of preparing the curable composition is not particularly limited. From the viewpoint of easily obtaining a curable composition in which solid components are uniformly dispersed, the cellulose-based fiber (C) is put into a stirrer into which water has been introduced and stirred, and the aluminosilicate (A) and alkaline metal water are stirred. It is preferable to add the oxide (B) and other powder (E) and the slag stimulant (F) when added, stir, and finally add the alkali-resistant fiber (D). The order of addition of the components (A) and (B) and the optional components (E) and (F) is not particularly limited.
- the amount of water is not particularly limited, but the solid content concentration in the step of preparing the curable composition is determined from the viewpoint that a uniform curable composition can be easily obtained without the curable composition containing excess water. Usually, it is 10% by mass or more and 25% by mass or less.
- the step of obtaining a molded plate by a papermaking method includes making a curable composition with a circular net.
- the solid content concentration in the step of preparing the curable composition is usually 10% by mass or more and 25% by mass or less.
- the prepared curable composition is usually diluted with process circulating water to a solid content concentration of 3% by mass or more and 10% by mass or less, and the diluted curable composition is supplied to a circular net and produced as a molded plate. increase.
- the solid content produced by a single circular net or 2 to 6 continuous circular nets is adhered to the felt to obtain a molded plate, which is wound with a making roll to have a desired thickness. Since the molded plates are laminated until they become, continuous production is possible.
- general procedures and conditions in the other circular network system general procedures and conditions can be adopted.
- two or more molded plates obtained by the papermaking method are laminated.
- a laminated molded plate is obtained by laminating with a making roll until the desired thickness is obtained, dehydrating and pressing, curing, and drying.
- the pressure of the dehydration press is usually 20 kg / cm 2 to 300 kg / cm 2 , and the pressurization holding time is usually 10 minutes to 60 minutes.
- Curing is usually carried out under the conditions of a temperature of 50 ° C. to 90 ° C. and a relative humidity of 80% to 100% for 8 hours to 55 hours.
- the drying method is not particularly limited as long as a uniformly dried laminated molded plate can be obtained.
- the equilibrium moisture content of the laminated molded plate (for example, the moisture content reached when stored in a well-ventilated room for 7 days or more) is about 6% to about 10%, so that the moisture content is about the same as the equilibrium moisture content. Dry so that it becomes.
- the water content and the equilibrium water content of the laminated molded plate can be simply measured using a Kett moisture meter.
- the laminated molded plate after drying is weighed (W 3 ), and then the laminated molded plate dried to a constant weight in an air dryer equipped with a stirrer at 105 ° C. is weighed (W 4 ), and the following formula: ⁇ (W 3- W 4 ) / W 4 ⁇ x 100 Can also be obtained by.
- the obtained laminated molded plate is based on a curable composition having excellent uniformity due to a specific composition, it can have high bending strength, high impact strength and high dimensional stability.
- the thickness of the laminated molded plate to be measured was measured at 6 points using a digital caliper, and the average value was taken as the thickness of the laminated molded plate.
- the bulk specific density was measured according to JIS A 5430. Specifically, the laminated molded plate to be measured was put into an air dryer equipped with a stirrer, dried at 105 ° C. ⁇ 5 ° C. for 24 hours, and then the bulk specific gravity was obtained from the mass and volume of the laminated molded plate.
- the dimensional change rate of the laminated molded plate was measured according to JIS A 5430. First, the laminated molded plate to be measured was placed in a dryer, the temperature was maintained at 60 ° C. ⁇ 3 ° C. for 24 hours, and then the plate was taken out. The taken-out laminated molded plate was placed in a desiccator whose humidity was controlled with silica gel, and left to stand until the temperature reached 20 ⁇ 1.5 ° C.
- a milk-colored glass is pasted on the laminated molded plate, the marked lines are carved so that the distance between the marked lines is about 140 mm, the length between the marked lines is measured with a comparator having an accuracy of 1/500 mm, and the length is measured.
- L 1 (mm) the laminated molded plate was erected so that the length direction was horizontal, and the laminated molded plate was immersed in water at 20 ° C. ⁇ 1.5 ° C. so that the upper end of the laminated molded plate was about 30 mm below the water surface.
- Example 1 3% by mass of pulp (NBKP, cellophane fiber manufactured by Partex Co., Ltd.) as a cellulosic fiber (C) was dispersed in water.
- the slurry was supplied to the circular net process from the feed tank of the fixed quantity supply device, the solid content concentration was adjusted to 4% by mass by the process circulating water, and papermaking was performed using a mini-ha check machine.
- 10 molded plates obtained in the circular net step were laminated with a making roller, and the laminated wet molded plates were pressed for 20 minutes while applying a pressure of 75 kg / cm 2 to squeeze the liquid.
- the thickness of the molded plate after being laminated and squeezed was 4.6 mm, and the bulk specific density was 1.35 g / cm 3 .
- This is laminated and molded by curing it in a constant temperature and humidity curing device at a temperature of 90 ° C. and saturated humidity (RH98%) for 48 hours, and then drying it in an air dryer with a stirrer at 60 ° C. for 16 hours. I got a board.
- the obtained laminated molded plate was evaluated as described above. The results are shown in Table 2.
- Example 2 A laminated molded plate was manufactured and evaluated in the same manner as in Example 1 except that the ratio of the blast furnace slag and the ratio of the alkaline metal hydroxide (B) were changed as shown in Table 2.
- Examples 5 to 7 A laminated molded plate was produced and evaluated in the same manner as in Example 3 except that the types of alkali-resistant fibers (D) other than the cellulosic fibers were changed as shown in Table 2.
- Example 8 Except for using blast furnace slag having a specific surface area of 6000 cm 2 / g in place of the blast furnace slag having a specific surface area of 4000 cm 2 / g in the same manner as in Example 2 to produce a laminated molded plate was evaluated ..
- Example 9 4000cm using blast furnace slag having a specific surface area of 6000 cm 2 / g in place of the blast furnace slag having a specific surface area of 2 / g, except for using PVA2 instead of PVA1 in the same manner as in Example 3, the laminated molding plate was manufactured and evaluated.
- Example 10 to 11 A laminated molded plate was manufactured and evaluated in the same manner as in Example 9 except that the ratio of blast furnace slag and the ratio of fly ash were changed as shown in Table 2.
- Example 12 to 13 A laminated molded plate was manufactured and evaluated in the same manner as in Example 11 except that the ratio of blast furnace slag and the ratio of silica fume were changed as shown in Table 2.
- Example 14 A laminated molded plate was manufactured and evaluated in the same manner as in Example 3 except that the ratio of blast furnace slag and the ratio of pulp were changed as shown in Table 2.
- Example 15 A laminated molded plate was manufactured and evaluated in the same manner as in Example 6 except that the ratio of the blast furnace slag and the ratio of the alkali-resistant fiber (D) other than the cellulosic fiber were changed as shown in Table 2. ..
- Example 16 In addition, silica fume and dihydrate gypsum were added instead of silica fume as powder (E), and the ratio of blast furnace slag and the ratio of alkaline metal hydroxide (B) were changed as shown in Table 2. A laminated molded plate was manufactured and evaluated in the same manner as in Example 1 except for the above.
- Example 17 The ratio of blast furnace slag and the ratio of alkaline metal hydroxide (B) were changed as shown in Table 2, and the dispersion of cellulose-based fiber (C) and the blast furnace as an aluminosilicate source (A). Instead of mixing slag and fly ash, slaked lime as an alkaline metal hydroxide (B), and silica fume as other powder (E) with a mixer, a dispersion of cellulose-based fibers (C). A laminated molded plate was produced and evaluated in the same manner as in Example 1 except that in addition to the above-mentioned material, aluminum sulfate as a slag stimulant (F) was mixed with a mixer.
- Table 2 The ratio of blast furnace slag and the ratio of alkaline metal hydroxide (B) were changed as shown in Table 2, and the dispersion of cellulose-based fiber (C) and the blast furnace as an aluminosilicate source (A).
- slaked lime as an alkaline
- Example 18 In addition, as the powder (E), silica fume and dihydrate gypsum were added instead of silica fume, and the ratio of blast furnace slag and the types of alkali-resistant fibers (D) other than cellulosic fibers are as shown in Table 2.
- a laminated molded plate was manufactured and evaluated in the same manner as in Example 2 except that the changes were made.
- Example 20 to 21 Table shows the addition of silica fume and dihydrate gypsum instead of silica fume as powder (E), the ratio of blast furnace slag, the ratio of alkaline metal hydroxide (B), and the ratio of slag stimulant (F).
- E silica fume and dihydrate gypsum
- B the ratio of alkaline metal hydroxide
- F the ratio of slag stimulant
- Example 22 The laminated molded plate was prepared in the same manner as in Example 1 except that fly ash and red mud were added instead of fly ash, and the ratio of blast furnace slag and the ratio of fly ash were changed as shown in Table 2. Manufactured and evaluated.
- Example 23 Examples except that fly ash and red mud were added instead of fly ash, and the ratio of blast furnace slag, the ratio of fly ash, and the ratio of silica fume were changed as shown in Table 2. In the same manner as in No. 4, a laminated molded plate was manufactured and evaluated.
- Example 24 Except that the proportion of blast furnace slag was changed from 75.5% by mass to 56% by mass, and the proportion of fly ash and the proportion of alkaline metal hydroxide (B) were changed as shown in Table 2. A laminated molded plate was manufactured and evaluated in the same manner as in Example 8.
- Example 2 A laminated molded plate was manufactured in the same manner as in Example 3 except that the alkali-resistant fiber (D) other than the cellulosic fiber was not added and the ratio of the blast furnace slag was changed as shown in Table 2. Evaluation was carried out.
- Example 6 The same as in Example 1 except that the ratio of blast furnace slag was changed from 80.5% by mass to 90.5% by mass, and the ratio of fly ash and the ratio of silica fume were changed as shown in Table 2. A laminated molded plate was manufactured and evaluated.
- Table 1 The characteristics of the fibers used in Examples and Comparative Examples are shown in Table 1 below.
- Table 2 shows the compositions in Examples and Comparative Examples, and the evaluation results of the laminated molded plate.
- All of the laminated molded plates produced in Examples 1 to 24 had high bending strength, high impact strength, and high dimensional stability.
- the laminated molded plate of Comparative Example 2 to which the alkali-resistant fiber (D) was not added showed extremely low bending strength and extremely low impact strength.
- a specific surface area of 1000 cm 2 / g or more, the laminated molding plate of 9000 cm 2 / g content of blast furnace slag or less is 55 mass% or less with respect to the total solid content of the curable composition Comparative Example 3 is significantly lower It showed impact strength and a significantly higher rate of dimensional change.
- the laminated molded plate of Comparative Example 4 containing blast furnace slag having a specific surface area of less than 1000 cm 2 / g in an amount of 60% by mass or more based on the total solid content of the curable composition has extremely low bending strength, extremely low impact strength and high dimensional change. Shown the rate.
- the laminated molded plate of Comparative Example 5 containing blast furnace slag having a specific surface area of more than 9000 cm 2 / g in an amount of 60% by mass or more based on the total solid content of the curable composition has extremely low bending strength, extremely low impact strength and high dimensional change. Shown the rate.
- a specific surface area of 1000 cm 2 / g or more, 9000 cm 2 / g content of blast furnace slag or less laminated molded plate is greater than 90 wt% Comparative Example 6 with respect to the total solid content of the curable composition, bend significantly lower It showed strength and high dimensional change rate.
- the laminated molded plate of the present invention has high bending strength, high impact strength and high dimensional stability. Therefore, the laminated molded plate of the present invention is not particularly limited, but as various building materials such as interior materials, exterior materials, floor materials, wall materials, ceiling materials, partitions, roofing materials and roof tiles. It can be used usefully.
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Abstract
Description
特許文献2には、断面充実度が40~70%であるポリビニルアルコール系繊維を全固形分中1.0~2.0質量%、濾水度100~500mlであるユーカリパルプを全固形分中2.0~4.0質量%各々含有してなり、層間密着強度が2.0N/mm2以上で、かつ寸法変化率が0.25%以下であることを特徴とするノンアスベスト水硬性抄造板が記載されている。
特許文献3には、(A)少なくとも一種のアルミノケイ酸塩源、(B)アルカリ金属水酸化物、(C)カルシウムイオン供給源および(D)耐アルカリ性繊維を含有する硬化性組成物から形成される成形体であって、アルミノケイ酸塩源(A)が特定のアルミノケイ酸塩源を含む成形体が記載されている。この成形体は、注型法、脱水成形法、射出成形法または押出成形法等の成形法により製造される成形体であって、同文献では、抄造法により製造される抄造板は対象とされていない。
上述した事情に鑑み、本発明は、繊維により補強された、高い曲げ強度、高い衝撃強度および高い寸法安定性を有する積層成形板を提供することを課題とする。
[1](A)アルミノケイ酸塩源、(B)アルカリ性の金属水酸化物、(C)セルロース系繊維および(D)セルロース系繊維以外の耐アルカリ性繊維を含んでなる硬化性組成物から形成される成形板を2枚以上含んでなる積層成形板であって、アルミノケイ酸塩源(A)は高炉スラグを含み、高炉スラグの比表面積が1000cm2/g以上、9000cm2/g以下である高炉スラグの含有率は、硬化性組成物の全固形分に対して55質量%を超え、90質量%以下である、積層成形板。
[2]アルカリ性の金属水酸化物(B)の含有率は、硬化性組成物の全固形分に対して3質量%以上、45質量%以下である、前記[1]に記載の積層成形板。
[3]セルロース系繊維(C)の含有率は、積層成形板の全固形分に対して0.5質量%以上、15質量%以下である、前記[1]または[2]に記載の積層成形板。
[4]セルロース系繊維以外の耐アルカリ性繊維(D)の含有率は、積層成形板の全固形分に対して0.1質量%以上、5質量%以下である、前記[1]~[3]のいずれかに記載の積層成形板。
[5]アルミノケイ酸塩源(A)は、フライアッシュ、メタカオリンおよび赤泥からなる群から選択される少なくとも1つを、硬化性組成物の全固形分に対して1質量%以上、35質量%以下の含有率で更に含む、前記[1]~[4]のいずれかに記載の積層成形板。
[6]アルカリ性の金属水酸化物(B)は消石灰である、前記[1]~[5]のいずれかに記載の積層成形板。
[7]セルロース系繊維(C)はパルプである、前記[1]~[6]のいずれかに記載の積層成形板。
[8]セルロース系繊維以外の耐アルカリ性繊維(D)の平均繊維径は100μm以下であり、アスペクト比は50以上、2000以下である、前記[1]~[7]のいずれかに記載の積層成形板。
[9]セルロース系繊維以外の耐アルカリ性繊維(D)は、ポリビニルアルコール系繊維、ポリエチレン繊維、ポリプロピレン繊維、アクリル繊維、アラミド繊維およびナイロン繊維からなる群から選択される少なくとも1つである、前記[1]~[8]のいずれかに記載の積層成形板。
[10]積層成形板のJIS K 7111に準拠して測定される衝撃強度は2kJ/m2以上である、前記[1]~[9]のいずれかに記載の積層成形板。
[11]アルミノケイ酸塩源(A)、アルカリ性の金属水酸化物(B)、セルロース系繊維(C)、セルロース系繊維以外の耐アルカリ性繊維(D)および水を混合して硬化性組成物を調製する工程、
得られた硬化性組成物を用いて抄造法により成形板を得る工程、および
得られた成形板を2枚以上積層する工程
を含む、前記[1]~[10]のいずれかに記載の積層成形板の製造方法。
[12]前記した抄造法により成形板を得る工程は、前記硬化性組成物を円網で抄き上げることを含む、前記[11]に記載の方法。
アルミノケイ酸塩源は、アルミノケイ酸塩(xM2O・yAl2O3・zSiO2・nH2O、Mはアルカリ金属)を主成分として含有する。ここで、主成分とは、アルミノケイ酸塩源中で最も質量の多い成分を意味する。アルミノケイ酸塩源は、高アルカリ性溶液〔アルカリ性の金属水酸化物(B)の水溶液〕との接触により、アルミニウムおよびケイ素等の陽イオンを溶出し、これらが重縮合することにより、強固なSiO4・AlO4のポリマーネットワークが形成される。
本発明で用いられるアルカリ性の金属水酸化物(B)は、水中で高アルカリ性を示し、前記アルミノケイ酸塩源(A)と接触すると、それを活性化させ、AlおよびSi等の陽イオンを溶出させる作用を有する。
本発明で用いられるセルロース系繊維(C)は、積層成形板の曲げ強度および衝撃強度を高める作用を有する。
本発明で用いられるセルロース系繊維以外の耐アルカリ性繊維(D)は、積層成形板の曲げ強度および衝撃強度を高める作用を有する。セルロース系繊維(C)と、セルロース系繊維以外の耐アルカリ性繊維(D)(以下において、「耐アルカリ性繊維(D)」と略記することがある)とを併用することにより、繊維による補強効果を相乗的に向上できることが見出された。
積層成形板における耐アルカリ性繊維(D)の含有率=(W2/W1)×100
本発明における積層成形板は、その他の粉体(E)として、アルミノケイ酸塩源(A)以外の粉体を更に含んでよい。その他の粉体(E)の例としては、シリカヒューム、炭酸カルシウム、ベントナイト、および硫酸カルシウム誘導体(例えば、二水石膏、排脱石膏、α型またはβ型の半水石膏、および無水石膏)を挙げることができ、これらを単独で、または2種以上組み合わせて使用してよい。積層成形板がシリカヒュームを含むと、積層成形板においてより優れた寸法安定性が達成されやすいため好ましい。
本発明における硬化体は、スラグ刺激剤(F)を更に含んでもよい。本発明における硬化性組成物にスラグ刺激剤(F)を添加すると、より高い曲げ強度を有する硬化体を得やすい。スラグ刺激剤(F)の例としては、硫酸アルミニウム、水酸化カルシウム、硫酸ナトリウムおよびアルミン酸ナトリウム等を挙げることができ、これらを単独で、または2種以上組み合わせて使用してよい。これらの中でも、より高い曲げ強度を有する硬化体を得やすい観点から、硫酸アルミニウム、水酸化カルシウムおよびアルミン酸ナトリウムからなる群から選択される1種以上を硬化体が含むことが好ましい。
本発明の積層成形板は、好ましくは抄造法により製造する。抄造法とは、アルミノケイ酸塩等の固体成分とセルロース系繊維(C)および耐アルカリ性繊維(D)等の繊維質成分とを水媒体に縣濁させたスラリー状の硬化性組成物をメッシュ上に抄き上げ、抄き上げた固形分を成形する方法である。抄造法の例としては、薄い板状の前記固形分を順次積層して所望の厚さの積層成形板を得る円網方式または長網方式、および濃厚な硬化性組成物を用いて1回ないし数回の抄き上げで、ある程度の厚さを確保するフローオン方式等を挙げることができる。抄造法では、機械的かつ連続的に、バッチ式で積層成形板を量産でき、製造される積層成形板は、均一で安定した性能を有することができる。また、通常2~30mm程度の比較的薄い板を製造することができる。このような比較的薄い板の製造は、抄造法以外の製造方法(例えば注型法)では極めて困難である。
アルミノケイ酸塩源(A)、アルカリ性の金属水酸化物(B)、セルロース系繊維(C)、セルロース系繊維以外の耐アルカリ性繊維(D)および水を混合して硬化性組成物を調製する工程、
得られた硬化性組成物を用いて抄造法により成形板を得る工程、および
得られた成形板を2枚以上積層する工程
を含む方法により製造することができる。
この製造方法において使用されるアルミノケイ酸塩源(A)、アルカリ性の金属水酸化物(B)、セルロース系繊維(C)およびセルロース系繊維以外の耐アルカリ性繊維(D)、並びに任意に用いてよいその他の粉体(E)およびスラグ刺激剤(F)としては、先の<(A)アルミノケイ酸塩源>、<(B)アルカリ性の金属水酸化物>、<(C)セルロース系繊維>、<(D)セルロース系繊維以外の耐アルカリ性繊維>、<(E)その他の粉体>および<(F)スラグ刺激剤>の段落において記載したものをそれぞれ使用することができる。
{(W3-W4)/W4}×100
により求めることもできる。
デジタル式ノギスを用いて、測定する積層成形板の厚さを6箇所測定し、その平均値を、積層成形板の厚さとした。
嵩比重は、JIS A 5430に準拠して測定した。具体的には、測定する積層成形板を撹拌機付き空気乾燥機に投入し、105℃±5℃で24時間乾燥した後の、積層成形板の質量および体積から嵩比重を求めた。
測定する積層成形板から、長さ約180mm、幅約50mmの短冊状の試験片を4個切り出した。その後、試験片の測定時の含水率を一定に調整するため、切り出した試験片を40℃に設定した撹拌機付き空気乾燥機において72時間乾燥した。各試験片の曲げ強度を、JIS A 1408に準拠して測定し、その平均値を曲げ強度として採用した。曲げ強度は、島津製作所株式会社製オートグラフ「AG500-B」を用い、中央載荷方式で曲げスパン14.6cmおよび試験速度(載荷ヘッドスピード)20mm/分の条件で測定した。
測定する積層成形板から、長さ約80mm、幅約10mmの短冊状の試験片を6個切り出した。その後、試験片の測定時の含水率を一定に調整するため、切り出した試験片を40℃に調整した撹拌機付き空気乾燥機において72時間乾燥した。各試験片の衝撃強度を、JIS K 7111「プラスチック-シャルピー衝撃強さの試験方法」に準拠して測定し、その平均値を衝撃強度として採用した。衝撃強度は、株式会社東洋精機製作所製、シャルピー(デジタル)衝撃試験機、型式DG-CBを用いて測定した。
積層成形板の寸法変化率は、JIS A 5430に準拠して測定した。
まず、測定する積層成形板を乾燥機に入れ、その温度を60℃±3℃で24時間を保った後、取り出した。取り出した積層成形板をシリカゲルで調湿したデシケータに入れ、20±1.5℃になるまで放置した。次に、積層成形板に乳色ガラスを貼り、標線間が約140mmになるように標線を刻み、1/500mmの精度を持つコンパレータで標線間の長さを測定し、その長さをL1(mm)とした。続いて、積層成形板の長さ方向が水平になるようこば立てし、積層成形板の上端が水面下約30mmとなるようにして、20℃±1.5℃の水中に浸漬した。24時間後、水中から積層成形板を取り出して表面に付着した水を拭き取り、標線間の長さを再び測定し、その長さをL2(mm)とした。下記式により、吸水による寸法変化率Y(%)を算出した。
吸水による長さ変化率Y={(L2-L1)/L1}×100
セルロース系繊維(C)としてのパルプ(NBKP、株式会社パルテックス製セロファイバー)3質量%を、水に分散させた。得られた分散体と、アルミノケイ酸塩源(A)としての高炉スラグ(比表面積4000cm2/g)80.5質量%およびフライアッシュ(四電ビジネス株式会社製:四電フライアッシュII種)5質量%、アルカリ性の金属水酸化物(B)としての消石灰(高知石灰工業株式会社製:工業用消石灰1号)5質量%、並びにその他の粉体(E)としてのシリカヒューム(巴工業株式会社製:EFACOシリカヒューム)5質量%とをミキサーで混合した。得られた混合物に、1.5質量%の耐アルカリ性繊維(D)としてのPVA1(株式会社クラレ製)を添加して更に混合し、固形分濃度16質量%のスラリー状の硬化性組成物を得た。得られた硬化性組成物を、定量供給装置に移送した。次いで、定量供給装置のフィードタンクから円網工程にスラリーを供給し、工程循環水によって固形分濃度を4質量%とし、ミニハチェックマシンを用いて抄造を行った。次いで、円網工程で得られた成形板をメーキングローラーにて10枚積層し、積層された湿潤状態の成形板を75kg/cm2の圧力を印加しながら20分間プレスすることにより搾液した。積層され、搾液した後の成形板の厚さは4.6mmであり、嵩比重は1.35g/cm3であった。これを、恒温恒湿養生装置において、温度90℃、飽和湿度(RH98%)条件下で48時間養生し、その後、撹拌機付き空気乾燥機において、60℃で16時間乾燥することにより、積層成形板を得た。
得られた積層成形板について、先に記載したように評価を実施した。結果を表2に示す。
高炉スラグの割合およびアルカリ性の金属水酸化物(B)の割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
セルロース系繊維以外の耐アルカリ性繊維(D)の種類を表2に記載の通りに変更したこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
4000cm2/gの比表面積を有する高炉スラグに代えて6000cm2/gの比表面積を有する高炉スラグを用いたこと以外は実施例2と同様にして、積層成形板を製造し、評価を実施した。
4000cm2/gの比表面積を有する高炉スラグに代えて6000cm2/gの比表面積を有する高炉スラグを用い、PVA1に代えてPVA2を用いたこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合およびフライアッシュの割合を表2に記載の通りに変更したこと以外は実施例9と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合およびシリカヒュームの割合を表2に記載の通りに変更したこと以外は実施例11と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合およびパルプの割合を表2に記載の通りに変更したこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合およびセルロース系繊維以外の耐アルカリ性繊維(D)の割合を表2に記載の通りに変更したこと以外は実施例6と同様にして、積層成形板を製造し、評価を実施した。
その他粉体(E)としてシリカヒュームに代えてシリカヒュームおよび二水石膏を加えたこと、並びに高炉スラグの割合およびアルカリ性の金属水酸化物(B)の割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合およびアルカリ性の金属水酸化物(B)の割合を表2に記載の通りに変更したこと、並びにセルロース系繊維(C)の分散体と、アルミノケイ酸塩源(A)としての高炉スラグおよびフライアッシュ、アルカリ性の金属水酸化物(B)としての消石灰、並びにその他の粉体(E)としてのシリカヒュームとをミキサーで混合したことに代えて、セルロース系繊維(C)の分散体と、前記材料に加えてスラグ刺激剤(F)としての硫酸アルミニウムとをミキサーで混合したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
その他粉体(E)としてシリカヒュームに代えてシリカヒュームおよび二水石膏を加えたこと、並びに高炉スラグの割合およびセルロース系繊維以外の耐アルカリ性繊維(D)の種類を表2に記載の通りに変更したこと以外は実施例2と同様にして、積層成形板を製造し、評価を実施した。
その他粉体(E)としてシリカヒュームに代えてシリカヒュームおよび二水石膏を加えたこと、高炉スラグの割合、アルカリ性の金属水酸化物(B)の割合およびスラグ刺激剤(F)の割合を表2に記載の通りに変更し、養生の温度および時間を90℃、48時間から60℃、24時間に変更したこと以外は実施例17と同様にして、積層成形板を製造し、評価を実施した。
フライアッシュに代えてフライアッシュおよび赤泥を加えたこと、並びに高炉スラグの割合およびフライアッシュの割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合を75.5質量%から56質量%に変更し、それに伴い、フライアッシュの割合およびアルカリ性の金属水酸化物(B)の割合を表2に記載の通りに変更したこと以外は実施例8と同様にして、積層成形板を製造し、評価を実施した。
アルカリ性の金属水酸化物(B)を添加せず、それに伴い高炉スラグの割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造しようとしたが、硬化しなかった。従って、積層成形板の評価を実施できなかった。
セルロース系繊維以外の耐アルカリ性繊維(D)を添加せず、それに伴い高炉スラグの割合を表2に記載の通りに変更したこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合を80.5質量%から55質量%に変更し、それに伴い、アルカリ性の金属水酸化物(B)の割合、セルロース系繊維(C)の割合およびセルロース系繊維以外の耐アルカリ性繊維(D)の割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
4000cm2/gの比表面積を有する高炉スラグに代えて800cm2/gの比表面積を有する高炉スラグを用いたこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
4000cm2/gの比表面積を有する高炉スラグに代えて10000cm2/gの比表面積を有する高炉スラグを用いたこと以外は実施例3と同様にして、積層成形板を製造し、評価を実施した。
高炉スラグの割合を80.5質量%から90.5質量%に変更し、フライアッシュの割合およびシリカヒュームの割合を表2に記載の通りに変更したこと以外は実施例1と同様にして、積層成形板を製造し、評価を実施した。
比表面積が1000cm2/g以上、9000cm2/g以下である高炉スラグの含有率が硬化性組成物の全固形分に対して55質量%以下である比較例3の積層成形板は、著しく低い衝撃強度および著しく高い寸法変化率を示した。
比表面積が1000cm2/gより小さい高炉スラグを硬化性組成物の全固形分に対して60質量%以上含む比較例4の積層成形板は、著しく低い曲げ強度、著しく低い衝撃強度および高い寸法変化率を示した。
比表面積が9000cm2/gより大きい高炉スラグを硬化性組成物の全固形分に対して60質量%以上含む比較例5の積層成形板は、著しく低い曲げ強度、著しく低い衝撃強度および高い寸法変化率を示した。
比表面積が1000cm2/g以上、9000cm2/g以下である高炉スラグの含有率が硬化性組成物の全固形分に対して90質量%より大きい比較例6の積層成形板は、著しく低い曲げ強度および高い寸法変化率を示した。
Claims (12)
- (A)アルミノケイ酸塩源、(B)アルカリ性の金属水酸化物、(C)セルロース系繊維および(D)セルロース系繊維以外の耐アルカリ性繊維を含んでなる硬化性組成物から形成される成形板を2枚以上含んでなる積層成形板であって、アルミノケイ酸塩源(A)は高炉スラグを含み、比表面積が1000cm2/g以上、9000cm2/g以下である高炉スラグの含有率は、硬化性組成物の全固形分に対して55質量%を超え、90質量%以下である、積層成形板。
- アルカリ性の金属水酸化物(B)の含有率は、硬化性組成物の全固形分に対して3質量%以上、45質量%以下である、請求項1に記載の積層成形板。
- セルロース系繊維(C)の含有率は、積層成形板の全固形分に対して0.5質量%以上、15質量%以下である、請求項1または2に記載の積層成形板。
- セルロース系繊維以外の耐アルカリ性繊維(D)の含有率は、積層成形板の全固形分に対して0.1質量%以上、5質量%以下である、請求項1~3のいずれかに記載の積層成形板。
- アルミノケイ酸塩源(A)は、フライアッシュ、メタカオリンおよび赤泥からなる群から選択される少なくとも1つを、硬化性組成物の全固形分に対して1質量%以上、35質量%以下の含有率で更に含む、請求項1~4のいずれかに記載の積層成形板。
- アルカリ性の金属水酸化物(B)は消石灰である、請求項1~5のいずれかに記載の積層成形板。
- セルロース系繊維(C)はパルプである、請求項1~6のいずれかに記載の積層成形板。
- セルロース系繊維以外の耐アルカリ性繊維(D)の平均繊維径は100μm以下であり、アスペクト比は50以上、2000以下である、請求項1~7のいずれかに記載の積層成形板。
- セルロース系繊維以外の耐アルカリ性繊維(D)は、ポリビニルアルコール系繊維、ポリエチレン繊維、ポリプロピレン繊維、アクリル繊維、アラミド繊維およびナイロン繊維からなる群から選択される少なくとも1つである、請求項1~8のいずれかに記載の積層成形板。
- 積層成形板のJIS K 7111に準拠して測定される衝撃強度は2kJ/m2以上である、請求項1~9のいずれかに記載の積層成形板。
- アルミノケイ酸塩源(A)、アルカリ性の金属水酸化物(B)、セルロース系繊維(C)、セルロース系繊維以外の耐アルカリ性繊維(D)および水を混合して硬化性組成物を調製する工程、
得られた硬化性組成物を用いて抄造法により成形板を得る工程、および
得られた成形板を2枚以上積層する工程
を含む、請求項1~10のいずれかに記載の積層成形板の製造方法。 - 前記した抄造法により成形板を得る工程は、前記硬化性組成物を円網で抄き上げることを含む、請求項11に記載の方法。
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WO2024069279A1 (en) * | 2022-09-26 | 2024-04-04 | Unilin, Bv | Method for producing a geopolymeric panel, and geopolymeric panel obtained therewith |
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US20230271881A1 (en) | 2023-08-31 |
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JPWO2022004640A1 (ja) | 2022-01-06 |
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