JP4927011B2 - Method for producing calcium silicate material - Google Patents
Method for producing calcium silicate material Download PDFInfo
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- JP4927011B2 JP4927011B2 JP2008077368A JP2008077368A JP4927011B2 JP 4927011 B2 JP4927011 B2 JP 4927011B2 JP 2008077368 A JP2008077368 A JP 2008077368A JP 2008077368 A JP2008077368 A JP 2008077368A JP 4927011 B2 JP4927011 B2 JP 4927011B2
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- calcium silicate
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- pulverized powder
- board
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- 239000000378 calcium silicate Substances 0.000 title claims description 71
- 229910052918 calcium silicate Inorganic materials 0.000 title claims description 71
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000463 material Substances 0.000 title description 7
- 239000002994 raw material Substances 0.000 claims description 74
- 239000002699 waste material Substances 0.000 claims description 55
- 239000010440 gypsum Substances 0.000 claims description 48
- 229910052602 gypsum Inorganic materials 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 45
- 239000011159 matrix material Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000011810 insulating material Substances 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 235000012241 calcium silicate Nutrition 0.000 description 65
- 229960003340 calcium silicate Drugs 0.000 description 65
- 230000032798 delamination Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000012774 insulation material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- -1 diatomaceous earth Chemical compound 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- 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
Landscapes
- Producing Shaped Articles From Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、原料の一部として石膏ボード廃材を使用したけい酸カルシウム板の製造方法に関するものである。 The present invention relates to a method for producing a calcium silicate plate using gypsum board waste as part of the raw material.
けい酸カルシウム板は、優れた寸法安定性、強度及び耐熱性等により、防火建材として広く使用されている。けい酸カルシウム板は、基本的にけい酸質原料と石灰質原料と必要に応じて補強繊維を原料としてスラリーを得、成形後オートクレーブ処理することにより製造される。そして、これに石膏を添加すると、けい酸カルシウム板の材質が曲がりやすくなる、すなわち柔らかくなることが知られている（特許文献１）。そして、その石膏原料として石膏ボード廃材の粉砕粉を用いれば優れた曲げ強度を有するけい酸カルシウム板が得られることが知られている（特許文献２）。
石膏ボード廃材を利用するけい酸カルシウム板は極めて大量に発生する石膏ボード廃材の有効利用という点、及びけい酸カルシウム板の性能向上から有用であるが、けい酸カルシウム板の製造方法として最も広く使用されている方法である抄造法により、原料の一部として石膏ボード廃材の粉砕粉を用いてけい酸カルシウム板を製造した場合、得られるけい酸カルシウム板が層間剥離を生じやすくなるという問題があることが判明した。
従って、本発明の目的は、原料の一部として石膏ボード廃材を使用して抄造法によりけい酸カルシウム板の製造する際の層間剥離を防止する手段を提供することにある。
Calcium silicate board using gypsum board waste is useful in terms of effective utilization of gypsum board waste generated in extremely large quantities and improved performance of calcium silicate board, but is most widely used as a manufacturing method for calcium silicate board When a calcium silicate board is produced by using the pulverized powder of gypsum board waste as a part of the raw material by the papermaking method, there is a problem that the obtained calcium silicate board tends to cause delamination It has been found.
Accordingly, an object of the present invention is to provide means for preventing delamination when a calcium silicate board is produced by a papermaking method using gypsum board waste as a part of raw materials.
そこで本発明者らは、けい酸カルシウム板の層間剥離を防止すべく種々検討した結果、全く意外にも、石膏ボード廃材粉砕粉に加えて、けい酸カルシウム保温材廃材粉砕粉を配合すれば、抄造法でけい酸カルシウム板を製造しても層間剥離が生じず、かつ成形性や物性の低下がなく、防火建材として有用なけい酸カルシウム板が得られることを見出し、本発明を完成した。 Therefore, as a result of various studies to prevent delamination of the calcium silicate plate, the present inventors surprisingly, in addition to the gypsum board waste material pulverized powder, in addition to the calcium silicate heat insulating material waste material pulverized powder, The present inventors have found that a calcium silicate plate that is useful as a fireproof building material can be obtained without causing delamination even when a calcium silicate plate is produced by a papermaking method, and without deterioration of formability and physical properties.
すなわち、本発明は、原料に水を加えて混合して原料スラリーを得、原料スラリーを抄造機にて抄造して薄膜を得、該薄膜を抄造機のメーキングロールに巻き取って所定の厚さまで積層した後メーキングロールから取り出して生板を得、生板をオートクレーブ養生して硬化させることからなるけい酸カルシウム板の製造方法において、原料として、マトリックス形成用原料３０〜９０質量％、繊維原料２〜１５質量％、石膏ボード廃材粉砕粉２〜５０質量％及びけい酸カルシウム保温材廃材粉砕粉１〜２０質量％を用いることを特徴とするけい酸カルシウム板の製造方法を提供するものである。 That is, in the present invention, water is added to a raw material and mixed to obtain a raw material slurry, the raw material slurry is made by a paper machine to obtain a thin film, and the thin film is wound around a making roll of the paper machine to a predetermined thickness. In the manufacturing method of the calcium silicate board which takes out from a making roll after lamination | stacking, obtains a green plate, cures a raw plate by autoclave curing, as a raw material, 30-90 mass% of raw materials for matrix formation, fiber raw material 2 The present invention provides a method for producing a calcium silicate plate characterized by using ~ 15 mass%, gypsum board waste material pulverized powder 2-50 mass%, and calcium silicate heat insulating material waste material pulverized powder 1-20 mass%.
本発明の製造方法を使用すれば、原料の一部として石膏ボード廃材を使用した場合であっても、層間剥離を生ずることなく抄造法によりけい酸カルシウム板を容易に製造することができる。また、本発明の製造方法を使用すれば、石膏ボード廃材とけい酸カルシウム保温材廃材の双方を有効利用することができる。なお、けい酸カルシウム保温材廃材をけい酸カルシウム板の原料として利用することは知られている（特許文献３）が、石膏ボード廃材と併用すること、さらに当該併用により石膏ボード廃材を使用した場合の層間剥離を防止できることは全く予想できなかったことである。 If the manufacturing method of this invention is used, even if it is a case where gypsum board waste material is used as a part of raw material, a calcium-silicate board can be easily manufactured by a papermaking method, without producing delamination. Moreover, if the manufacturing method of this invention is used, both a gypsum board waste material and a calcium silicate heat insulating material waste material can be utilized effectively. In addition, it is known to use calcium silicate thermal insulation waste as a raw material for calcium silicate board (Patent Document 3), but when used together with gypsum board waste, and when using gypsum board waste due to the combined use It was impossible to predict that delamination could be prevented.
以下、本発明の特徴及びそれによる作用効果について、実施の形態によってさらに詳しく説明する。 Hereinafter, the features of the present invention and the operational effects thereof will be described in more detail with reference to embodiments.
本発明により製造されるけい酸カルシウム板は、けい酸カルシウム水和物結晶である、トバモライト及び／又はゾノトライトをマトリックスとする材料である。このマトリックスを形成する原料は、石灰質原料及びけい酸質原料であり、いずれも従来から公知の原料を使用する。具体的には、石灰質原料としては、従来公知の消石灰、生石灰等を用いる。けい酸質原料としては、従来公知の珪石粉末等の結晶質シリカ、並びにけいそう土、シリカヒューム及びホワイトカーボン等の非晶質シリカを用いる。また、ポルトランドセメントは、カルシウム成分とシリカ成分の両方を有するので、石灰質原料とけい酸質原料とを兼ねた原料として使用することができる。 The calcium silicate plate produced according to the present invention is a material based on tobermorite and / or zonotrite, which are calcium silicate hydrate crystals. The raw materials for forming this matrix are calcareous raw materials and siliceous raw materials, both of which are conventionally known raw materials. Specifically, conventionally known slaked lime, quicklime, etc. are used as the calcareous material. As the siliceous raw material, conventionally known crystalline silica such as silica powder and amorphous silica such as diatomaceous earth, silica fume and white carbon are used. Moreover, since Portland cement has both a calcium component and a silica component, it can be used as a raw material which combined the calcareous raw material and the siliceous raw material.
マトリックス形成原料は、後述するオートクレーブ養生により、トバモライト及び／又はゾノトライトを主体とするけい酸カルシウム水和物結晶を生成して、けい酸カルシウム板のマトリックスを形成するための原料である。主としてトバモライトをマトリックスとする場合は、石灰質原料及びけい酸質原料のＣａＯとＳｉＯ2のモル比（以下、Ｃ／Ｓと表す）が０．６から０．９の範囲となるように、石灰質原料及びけい酸質原料の配合比率を定める。また、主としてゾノトライトをマトリックスとする場合は、Ｃ／Ｓが０．９から１．０の範囲となるように、石灰質原料及びけい酸質原料の配合比率を定める。なお、マトリックスはトバモライトとゾノトライトの混晶を主体とするものであってもよい。 The matrix-forming raw material is a raw material for forming a calcium silicate plate matrix by producing calcium silicate hydrate crystals mainly composed of tobermorite and / or zonotlite by autoclave curing described later. When tobermorite is mainly used as the matrix, the calcareous raw material and the siliceous raw material so that the molar ratio of CaO and SiO 2 (hereinafter referred to as C / S) is in the range of 0.6 to 0.9. And the mixing ratio of siliceous raw materials. Further, when zonotolite is mainly used as a matrix, the blending ratio of the calcareous raw material and the siliceous raw material is determined so that C / S is in the range of 0.9 to 1.0. The matrix may be mainly composed of a mixed crystal of tobermorite and zonotolite.
原料の固形分全体に占めるマトリックス原料の配合比率は、３０〜９０質量％であり、より好ましくは３０〜７０質量％である。３０質量％未満であると、マトリックスが少なくなり、けい酸カルシウム板の強度が不十分となることから好ましくない。また、９０質量％を上回ると、製造や物性には問題はないが、石膏ボード廃材やけい酸カルシウム保温材廃材の使用量が少なくなるので、本発明の目的にそぐわない。 The mixing ratio of the matrix raw material in the total solid content of the raw material is 30 to 90% by mass, more preferably 30 to 70% by mass. If it is less than 30% by mass, the matrix is decreased, and the strength of the calcium silicate plate is insufficient, which is not preferable. On the other hand, if it exceeds 90% by mass, there is no problem in production and physical properties, but the amount of gypsum board waste and calcium silicate thermal insulation waste is reduced, so that it does not meet the purpose of the present invention.
繊維原料は、抄造法によりけい酸カルシウム板を製造する場合に用いられてきた、従来より公知の繊維を使用することができる。一般には、セルロースパルプを主体とするが、必要に応じて耐オートクレーブ性を有する他の繊維（例えば、ポリプロピレン繊維、ポリアクリロニトリル繊維等）を併用してもよい。原料の固形分全体に占める繊維原料の配合比率は、２〜１５質量％であり、より好ましくは３〜１０質量％である。２質量％未満であると、抄造において排水中への粉体原料の流出が多くなり稼働状態が不安定になり、けい酸カルシウム板の強度も不十分となることから好ましくない。また、１５質量％を上回ると、他の原料とともに水と混合して原料スラリーを形成する際の繊維原料の分散性が低下するので好ましくない。また、前記した繊維原料は有機物であるが、原料の固形分全体に占める有機分の量は、目的とするけい酸カルシウム板の不燃性（不燃、準不燃、難燃等）によって、上限値が定まる。不燃の場合、原料全体に占める有機分の量は、概ね１０質量％以下である。なお、かつては石綿が、けい酸カルシウム板の代表的な繊維原料であったが、現在は使用が禁止されている。 As the fiber raw material, conventionally known fibers that have been used in the case of producing a calcium silicate plate by a papermaking method can be used. In general, cellulose pulp is mainly used, but other fibers having autoclave resistance (for example, polypropylene fiber, polyacrylonitrile fiber, etc.) may be used in combination as necessary. The mixing ratio of the fiber raw material in the entire solid content of the raw material is 2 to 15% by mass, and more preferably 3 to 10% by mass. If it is less than 2% by mass, outflow of the powder raw material into the waste water in papermaking increases, the operation state becomes unstable, and the strength of the calcium silicate plate becomes insufficient. Moreover, when it exceeds 15 mass%, since the dispersibility of the fiber raw material at the time of mixing with water with other raw materials and forming a raw material slurry falls, it is unpreferable. Moreover, although the above-mentioned fiber raw material is an organic substance, the upper limit of the amount of organic content in the total solid content of the raw material depends on the incombustibility (non-combustion, semi-incombustibility, flame retardant, etc.) of the target calcium silicate plate. Determined. In the case of nonflammability, the amount of organic content in the entire raw material is approximately 10% by mass or less. In the past, asbestos was a typical fiber raw material for calcium silicate board, but its use is now prohibited.
石膏ボード廃材には、石膏ボード製造の際発生する廃材や建築現場等から生ずる石膏ボードの廃材があるが、本発明にはいずれも使用することができる。石膏ボード廃材は、公知の粉砕機（例えば、(株)奈良機械製作所製 自由粉砕機）で粉砕して粉砕粉として使用する。石膏ボード廃材は、石膏ボード原紙と石膏とに分別し、分別した石膏を粉砕して粉砕粉を得てもよく、あるいは分別することなく粉砕して粉砕粉を得てもよい。石膏ボード廃材粉砕粉の平均粒子径は、１５〜１００μｍが好ましく、２０〜７５μｍがさらに好ましい。１５μｍ未満であると、抄造において排水中に流出する量が多くなること、及び抄造時にろ水性が低下するという問題があることから好ましくない。１００μｍを上回ると、原料スラリー中で他の原料と分離しやすくなるので抄造性が低下すること、及び得られたけい酸カルシウム板を研磨加工する場合、表面の石膏ボード廃材粉砕粉が取れてしまうことにより穴を形成しやすく、表面不良となることから好ましくない。原料の固形分全体に占める石膏ボード廃材粉砕粉の配合比率は２〜５０質量％が好ましく、５〜３５質量％がさらに好ましい。２質量％未満であると、けい酸カルシウム板の製造や物性には問題はないが、石膏ボード廃材粉砕粉やけい酸カルシウム保温材廃材粉砕粉の配合比率が低下することになり、本発明の目的にそぐわない。また、けい酸カルシウム板の原料として石膏を使用した場合、けい酸カルシウム板の材質が柔らかくなることが知られており、石膏ボード廃材粉砕粉の量が５０質量％を上回ると、材質が柔らかくなりすぎて、天井等に施工した場合、施工後にけい酸カルシウム板に変形（垂れ）が発生することがあるので好ましくない。 The gypsum board waste material includes a waste material generated in the production of gypsum board and a gypsum board waste material generated from a construction site, and any of them can be used in the present invention. The gypsum board waste is pulverized with a known pulverizer (for example, a free pulverizer manufactured by Nara Machinery Co., Ltd.) and used as pulverized powder. The gypsum board waste material may be separated into gypsum board base paper and gypsum, and the separated gypsum may be pulverized to obtain a pulverized powder, or may be pulverized without separation to obtain a pulverized powder. The average particle size of the gypsum board waste material pulverized powder is preferably 15 to 100 μm, and more preferably 20 to 75 μm. If it is less than 15 μm, it is not preferred because there are problems that the amount flowing out into the waste water in papermaking increases and the freeness is lowered during papermaking. If it exceeds 100 μm, it becomes easy to separate from other raw materials in the raw slurry, so that the papermaking property is lowered, and when the obtained calcium silicate plate is polished, the gypsum board waste material ground powder on the surface can be removed. This is not preferable because a hole is easily formed and the surface becomes defective. 2-50 mass% is preferable, and, as for the mixture ratio of the gypsum board waste material pulverized powder to the whole solid content of a raw material, 5-35 mass% is more preferable. If it is less than 2% by mass, there is no problem in the production and physical properties of the calcium silicate plate, but the mixing ratio of the gypsum board waste material pulverized powder and the calcium silicate heat insulating material waste material pulverized powder will be reduced. Not fit for purpose. In addition, when gypsum is used as a raw material for calcium silicate board, it is known that the material of calcium silicate board becomes soft, and when the amount of ground gypsum board waste powder exceeds 50% by mass, the material becomes soft. Too much and it is not preferable to construct on the ceiling or the like because the calcium silicate plate may be deformed (sagging) after construction.
けい酸カルシウム保温材は、配管の断熱用等に使用されている材料であり、主としてトバモライトをマトリックスとするものと主としてゾノトライトをマトリックスとするものとがあるが、本発明にはいずれも使用することができる。また、けい酸カルシウム保温材廃材には、けい酸カルシウム保温材の製造の際発生する廃材や建築現場やメンテナンス等に伴って生ずるけい酸カルシウム保温材の廃材があるが、本発明にはいずれも使用することができる。 Calcium silicate thermal insulation is a material used for heat insulation of pipes, and there are mainly tobermorite as a matrix and mainly zonotrite as a matrix, but both are used in the present invention. Can do. In addition, the waste materials of calcium silicate heat insulation materials include waste materials generated in the manufacture of calcium silicate heat insulation materials and waste materials of calcium silicate heat insulation materials generated in connection with construction sites and maintenance. Can be used.
けい酸カルシウム保温材の廃材は、公知の粉砕機（例えば、(株)奈良機械製作所製 自由粉砕機）で粉砕して粉砕粉として使用する。本発明では、けい酸カルシウム保温材粉砕粉の平均粒子径を１００〜５００μｍとすることが好ましく、さらに好ましくは１５０〜３００μｍである。粒度が１００μｍ未満であると、抄造時にろ水性が低下するという問題があり好ましくない。また、粒度が５００μｍを上回ると、これが製品表面に露出した場合外観上好ましくない。原料の固形分全体に占めるけい酸カルシウム保温材粉砕粉の配合比率は、１〜２０質量％が好ましく、２〜１５質量％がさらに好ましい。１質量％未満であると、石膏ボード廃材粉砕粉を原料の一部に使用してけい酸カルシウム板を抄造法により製造した場合の問題点である層間剥離を防止する効果が低下するため好ましくない。また、２０質量％を上回ると、抄造時のろ水性低下という問題があり好ましくない。 The waste material of the calcium silicate heat insulating material is pulverized by a known pulverizer (for example, a free pulverizer manufactured by Nara Machinery Co., Ltd.) and used as pulverized powder. In this invention, it is preferable that the average particle diameter of a calcium silicate heat insulating material pulverized powder shall be 100-500 micrometers, More preferably, it is 150-300 micrometers. If the particle size is less than 100 μm, there is a problem that the freeness is lowered during papermaking, which is not preferable. On the other hand, when the particle size exceeds 500 μm, it is not preferable in appearance when it is exposed on the product surface. 1-20 mass% is preferable and, as for the mixture ratio of the calcium silicate heat insulating material pulverization powder which occupies for the whole solid content of a raw material, 2-15 mass% is more preferable. If it is less than 1% by mass, the effect of preventing delamination, which is a problem when a calcium silicate board is produced by a papermaking method using crushed powder of gypsum board waste as a part of the raw material, is not preferable. . Moreover, when it exceeds 20 mass%, there exists a problem of the drainage fall at the time of papermaking, and is unpreferable.
けい酸カルシウム保温材粉砕粉を使用すると、石膏ボード廃材粉砕粉を原料の一部に使用してけい酸カルシウム板を抄造法により製造した場合の問題点である層間剥離を防止することができる理由は明らかではないが、本発明者の考えは次のとおりである。まず、石膏ボード廃材粉砕粉を使用した場合に層間剥離が生じやすくなる理由であるが、抄造機によって形成される薄膜（グリーンフィルム）が脱水しやすい状態になり、グリーンフィルムをメーキングロールに巻き取る際、水分が容易に脱水され、積層されたグリーンフィルム同士が密着しにくくなるものと考えられる。これに対してけい酸カルシウム保温材廃材粉砕粉には、グリーンフィルムをメーキングロールに巻き取る際水分の脱水を抑制する効果があり、両者を併用することにより、メーキングロールに巻き取られ積層されたグリーンフィルム同士に密着が向上し、層間剥離が防止されるものと考えられる。このことをけい酸カルシウム保温材廃材を使用するという立場から考えれば、けい酸カルシウム保温材廃材粉砕粉を原料の一部として使用した場合、その配合量が増加すると、ろ水性が低下し成形性が悪化することを、石膏ボード廃材粉砕粉を配合することにより緩和することができると考えられる。 The reason why the use of pulverized calcium silicate thermal insulation powder can prevent delamination, which is a problem when calcium silicate board is manufactured by papermaking method using crushed powder of gypsum board waste as part of the raw material The idea of the present inventor is as follows. First, when using gypsum board waste material pulverized powder, delamination tends to occur, but the thin film (green film) formed by the papermaking machine becomes easy to dehydrate, and the green film is wound around a making roll. At this time, it is considered that moisture is easily dehydrated and the stacked green films are hardly adhered to each other. On the other hand, calcium silicate heat insulation material waste powder pulverized powder has the effect of suppressing the dehydration of water when the green film is wound around the making roll. By using both of them, the powder was wound around the making roll and laminated. It is considered that adhesion between green films is improved and delamination is prevented. Considering this from the standpoint of using calcium silicate heat insulating material waste, when calcium silicate heat insulating material pulverized powder is used as a part of the raw material, if its blending amount increases, the freeness decreases and the moldability It is thought that the worsening of the effect can be mitigated by blending gypsum board waste material pulverized powder.
これらの必須原料に加え、必要に応じて充填材を原料として使用することができる。充填材としては、ウォラストナイトやマイカ、炭酸カルシウム、等の鉱物性粉末、けい酸カルシウム板等の建材製品のリサイクル品粉砕物等がある。ウォラストナイトやマイカはけい酸カルシウム板の耐熱性、特に加熱を受けた際の膨張収縮を抑制する原料として用いられる。原料の固形分全体に占める充填材の配合比率は、５０質量％以下である。５０質量％を上回ると、石膏ボード廃材粉砕粉やけい酸カルシウム保温材廃材粉砕粉の配合比率が低下することになり、本発明の目的にそぐわない。 In addition to these essential raw materials, a filler can be used as a raw material as needed. Examples of the filler include mineral powders such as wollastonite, mica, and calcium carbonate, and pulverized products of building materials such as calcium silicate plates. Wollastonite and mica are used as a raw material for suppressing the heat resistance of the calcium silicate plate, particularly the expansion and contraction when heated. The blending ratio of the filler in the entire solid content of the raw material is 50% by mass or less. If it exceeds 50% by mass, the mixing ratio of the gypsum board waste material pulverized powder and the calcium silicate heat insulating material waste material pulverized powder is lowered, which is not suitable for the purpose of the present invention.
次に、抄造法によるけい酸カルシウム板の製造方法について説明する。まず、前記した原料に水を加えて混合し、原料スラリーを形成する。原料スラリーの好適な濃度は、後述する抄造法の種類によっても異なるが、混合を完了した時点では概ね１０〜２０％であり、抄造機に投入する際、必要に応じて割り水を加え濃度を調整する。なお、本願における原料スラリーの濃度は、各原料の固形分の質量の総和／（各原料の固形分の質量の総和＋水の質量）×１００（％）である。 Next, the manufacturing method of the calcium silicate board by a papermaking method is demonstrated. First, water is added to the above raw materials and mixed to form a raw material slurry. The suitable concentration of the raw slurry varies depending on the type of papermaking method to be described later, but is approximately 10 to 20% at the time of completion of mixing. adjust. In addition, the density | concentration of the raw material slurry in this application is the sum total of the mass of the solid content of each raw material / (sum of the mass of the solid content of each raw material + the mass of water) x 100 (%).
濃度調整された原料スラリーは抄造機にて抄き取られ、薄膜（グリーンフィルム）を形成する。抄造法としては、抄き箱（通称バット）中に原料スラリーを投入し、所定の目開きのメッシュを有するシリンダーで抄き取る丸網式抄造法や、エンドレスフェルト上に原料スラリーを供給して脱水しグリーンフィルムを形成するフローオン式抄造法等があるが、本発明ではいずれも使用することができる。 The raw material slurry whose concentration is adjusted is picked up by a paper making machine to form a thin film (green film). As the paper making method, the raw material slurry is put into a paper box (commonly called bat), and the paper is made with a cylinder having a mesh with a predetermined mesh, or the raw material slurry is supplied onto an endless felt. Although there is a flow-on papermaking method in which a green film is dehydrated, any of them can be used in the present invention.
形成されたグリーンフィルムは、抄造機のメーキングロールに巻き取られ、所定の厚さになるまで積層される。積層されるグリーンフィルムの層数は特に限定されるものではないが、厚さ６ｍｍのけい酸カルシウム板の場合、４〜６層である。グリーンフィルムはメーキングロールに所定の厚さまで積層された後取り出され、生板（グリーンシート）を形成する。 The formed green film is wound up on a making roll of a papermaking machine and laminated until a predetermined thickness is reached. The number of green film layers to be laminated is not particularly limited, but is 4 to 6 in the case of a 6 mm thick calcium silicate plate. The green film is laminated on a making roll to a predetermined thickness and then taken out to form a green board.
形成されたグリーンシートは、必要に応じて常温にて６〜２４時間、一次養生を行う。次いで、オートクレーブを用いてオートクレーブ養生を行う。オートクレーブ養生を行うことにより石灰質原料とけい酸質原料とが反応し、マトリックスとなるけい酸カルシウム水和物結晶を形成し硬化する。オートクレーブ養生の条件は、マトリックスがトバモライトを主体とする場合は、１６０℃〜１９０℃の飽和水蒸気圧下で３時間〜１５時間、マトリックスがゾノトライトを主体とする場合は、１９０℃〜２２０℃の飽和水蒸気圧下で３時間〜１５時間である。オートクレーブ養生を終了した後、必要に応じて乾燥や表面研磨等の加工が行われ、製品となる。 The formed green sheet is subjected to primary curing at room temperature for 6 to 24 hours as necessary. Subsequently, an autoclave curing is performed using an autoclave. By performing autoclave curing, the calcareous raw material and the silicic acid raw material react to form calcium silicate hydrate crystals serving as a matrix and harden. The autoclave curing conditions are 3 to 15 hours under saturated water vapor pressure of 160 to 190 ° C. when the matrix is mainly composed of tobermorite, and 190 to 220 ° C. saturated water vapor when the matrix is mainly composed of zonotolite. 3 to 15 hours under pressure. After the autoclave curing is completed, processing such as drying and surface polishing is performed as necessary to obtain a product.
次に実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to this.
実施例１〜８及び比較例１〜３
表１の条件（配合条件）に記載した原料の組成に基づき、マトリックス形成用原料、繊維原料、石膏ボード廃材粉砕粉、及びけい酸カルシウム保温材廃材粉砕粉を配合して配合物を得、水を加えて濃度５％のスラリーとした。次に、該スラリーを定法により成形して成形体を得た。かかる成形体を常温の湿空状態で１５時間一次養生した。一次養生後、表１記載の条件にてオートクレーブ養生して硬化させ、さらに、大気圧下１５０℃で５時間乾燥処理を行って６ｍｍ×９１０ｍｍ×１８２０ｍｍのけい酸カルシウム板を得た。
乾燥処理終了後に、複数の検査員で目視による層間剥離、フクレ、パンク等の不良発生有無について表面検査を行い、良否を選別した。
また、得たけい酸カルシウム板について見掛け密度、及び曲げ強度を測定した。
Examples 1-8 and Comparative Examples 1-3
Based on the composition of the raw materials described in the conditions (blending conditions) of Table 1, a raw material for matrix formation, fiber raw material, gypsum board waste material pulverized powder, and calcium silicate heat insulating material waste material pulverized powder are blended to obtain a composition, water Was added to obtain a slurry having a concentration of 5%. Next, the slurry was molded by a conventional method to obtain a molded body. Such a molded body was subjected to primary curing for 15 hours in a humid atmosphere at room temperature. After the primary curing, curing was carried out by curing in an autoclave under the conditions described in Table 1, and further a drying treatment was performed at 150 ° C. for 5 hours under atmospheric pressure to obtain a 6 mm × 910 mm × 1820 mm calcium silicate plate.
After completion of the drying process, a plurality of inspectors conducted a surface inspection for occurrence of defects such as visual delamination, blistering, and puncture, and selected pass / fail.
Further, the apparent density and bending strength of the obtained calcium silicate plate were measured.
石膏ボード廃材粉砕粉；石膏ボード廃材の紙と石膏分とを分離し、石膏分を粉砕したもの。平均粒子径は、５０μｍのものを使用した。粉末Ｘ線回折の結果、組成は殆どが二水石膏であるが、半水石膏、及び無水石膏もわずかな量であるが共存している。また、使用した石膏ボード廃材粉砕粉は粉砕の第一段階で紙と石膏とを分離し、石膏分のみを粉砕したものであるが熱分析の結果、０．８〜１．５質量％の石膏ボードの表裏面紙に由来したパルプと考えられる有機分を含有していた。 Gypsum board waste material pulverized powder: Gypsum board waste material paper and gypsum content separated and gypsum content crushed. An average particle size of 50 μm was used. As a result of powder X-ray diffraction, the composition is mostly dihydrate gypsum, but a small amount of hemihydrate gypsum and anhydrous gypsum coexist. Moreover, the used gypsum board waste powder was obtained by separating paper and gypsum in the first stage of crushing and crushing only the gypsum content. As a result of thermal analysis, 0.8 to 1.5% by mass of gypsum was obtained. It contained an organic component thought to be pulp derived from the front and back paper of the board.
けい酸カルシウム保温材廃材粉砕粉；奈良式粉砕機（自由粉砕機 Ｍ−５、外輪なし）を使用し、粗砕したゾノトライト系、及びトバモライト系保温材廃材を粉砕したもの。ゾノトライト系、及びトバモライト系の区別は粉末Ｘ線回折で行った。平均粒子径は１５０μｍのものを使用した。 Calcium silicate thermal insulation waste material pulverized powder: crushed crushed zonotolite and tobermorite thermal insulation waste using a Nara type pulverizer (free pulverizer M-5, no outer ring). The distinction between zonotlite and tobermorite was performed by powder X-ray diffraction. An average particle size of 150 μm was used.
なお、ここでいう平均粒子径とは、ふるいの目開きが６００μｍ、３００μｍ、１５０μｍ、９０μｍ、４５μｍのふるいと下皿とを、目開きが大きいふるいが上になるように積み重ねてロータップ式試験機に設置し、目開き６００μｍのふるい上に石膏ボード廃材粉砕粉あるいはけい酸カルシウム保温材廃材粉砕粉を入れ、１０分間ふるい分けた後、各ふるいにおける残分（質量％）を測定し、各ふるいの目開きの値を、各ふるいの残分の質量比により加重平均して求めた値である。 The average particle size here is a low-tap type tester in which sieves with a sieve opening of 600 μm, 300 μm, 150 μm, 90 μm, and 45 μm are stacked together with a lower plate so that the sieve with a large opening is on top. Place the crushed gypsum board waste powder or calcium silicate thermal insulation waste powder on a sieve with an opening of 600μm, and screen for 10 minutes. Then, measure the remaining amount (mass%) of each sieve. It is the value which calculated | required the value of mesh opening by the weighted average by the mass ratio of the remainder of each sieve.
表１から明らかなように、けい酸カルシウム板の製法に際し、石膏ボード廃材粉砕粉だけでなく、けい酸カルシウム保温材廃材粉砕粉を配合すれば、層間剥離を殆ど発生することなく、かつ物性の良好なけい酸カルシウム板が得られることがわかる。 As is apparent from Table 1, when the calcium silicate plate is produced, if not only the gypsum board waste material pulverized powder but also the calcium silicate heat insulation material pulverized powder is blended, almost no delamination occurs and the physical properties It can be seen that a good calcium silicate plate can be obtained.
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