JPH0485023A - Manufacture porous hollow composite sheet - Google Patents
Manufacture porous hollow composite sheetInfo
- Publication number
- JPH0485023A JPH0485023A JP20268690A JP20268690A JPH0485023A JP H0485023 A JPH0485023 A JP H0485023A JP 20268690 A JP20268690 A JP 20268690A JP 20268690 A JP20268690 A JP 20268690A JP H0485023 A JPH0485023 A JP H0485023A
- Authority
- JP
- Japan
- Prior art keywords
- porous hollow
- cement
- sheet
- plate
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000004568 cement Substances 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 6
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011398 Portland cement Substances 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- 229920002972 Acrylic fiber Polymers 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005452 bending Methods 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 6
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010425 asbestos Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229910052895 riebeckite Inorganic materials 0.000 description 5
- 239000001593 sorbitan monooleate Substances 0.000 description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 description 5
- 229940035049 sorbitan monooleate Drugs 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 239000011120 plywood Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- PHDVPEOLXYBNJY-KTKRTIGZSA-N 2-(2-hydroxyethoxy)ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCO PHDVPEOLXYBNJY-KTKRTIGZSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000011400 blast furnace cement Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011090 solid board Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- 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
- PWVUXRBUUYZMKM-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCO PWVUXRBUUYZMKM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、表裏面に板状物シート状物が貼着された、ア
スベスト繊維を含まない、安全性の高いセメント系多孔
中空複合板の製造方法に関するものである。本発明の方
法で得られた多孔中空複合板は、防火性、軽量性、安全
性、意匠性、耐折曲性に優れているので建築物の内装板
に適しているものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a highly safe cement-based porous hollow composite board that does not contain asbestos fibers and has plate-like sheet materials adhered to its front and back surfaces. This relates to a manufacturing method. The porous hollow composite board obtained by the method of the present invention has excellent fire resistance, light weight, safety, design, and bending resistance, and is therefore suitable for use as an interior board for buildings.
[従来の技術]
従来、無機質系複合板はアスベスト繊維で補強サレ?、
: 発泡セメント板に金属板を貼着したもの、又は実加
工などを施した金属板にセメントスラリーを流し込んで
硬化させた物が一般的であった。[Conventional technology] Previously, inorganic composite boards were reinforced with asbestos fibers? ,
: Commonly, a metal plate was attached to a foamed cement board, or a metal plate that had undergone actual processing was poured with cement slurry and allowed to harden.
[発明が解決しようとする課R]
上記従来のアスベストで補強された無機質系複合板は、
アスベスト繊維が人体の健康を損なう危険性が大きいた
め非アスベスト化が強く求められていた。[Problem R to be solved by the invention] The above-mentioned conventional asbestos-reinforced inorganic composite board has the following problems:
Because asbestos fibers pose a significant risk to human health, there has been a strong demand for asbestos-free materials.
又上記従来の金属板を貼着したセメント複合板はセメン
ト複合板と接着剤のなじみが悪いため金属板との接着性
に劣り、金属板による補強効果が十分に得られないもの
であった。In addition, the conventional cement composite board to which the metal plate is attached has poor adhesion to the metal plate due to poor compatibility between the cement composite board and the adhesive, and the reinforcement effect of the metal plate cannot be obtained sufficiently.
又実加工などの施された金属板にセメントスラリーを流
し込んで硬化させた複合板は、金属板との強い接着は期
待できないので長尺物は生産が困難であった。Furthermore, composite plates made by pouring cement slurry into a metal plate that has been subjected to actual processing and curing cannot be expected to have strong adhesion to the metal plate, making it difficult to produce long pieces.
[課題を解決するための手段]
本発明は、重合開始剤と逆乳化剤を含有する非水溶性の
とニルモノマーとセメントと水と合成繊維とから得られ
る補強繊維が分散されたセメント含有W/O型エマルジ
ョンを多孔中空状に押出成形し、自然養生、蒸気養生あ
るいはオートクレーブ養生により、ビニルモノマーの重
合反応と、セメントの水和反応とを進行させて硬化した
後乾燥し、表裏面に板上物又はシート状物を貼着し、軽
量で防火性、安全性、意匠性、耐折曲性の優れた多孔中
空複合板を得る方法を提供するものである。[Means for Solving the Problems] The present invention provides a cement-containing W/O in which reinforcing fibers obtained from a water-insoluble monomer containing a polymerization initiator and an inverse emulsifier, cement, water, and synthetic fibers are dispersed. The mold emulsion is extruded into a porous hollow shape, and cured by natural curing, steam curing, or autoclave curing to advance the polymerization reaction of vinyl monomer and the hydration reaction of cement. After hardening, it is dried, and a plate-like material is formed on the front and back surfaces. Alternatively, the present invention provides a method for obtaining a lightweight, porous hollow composite plate having excellent fire resistance, safety, design, and bending resistance by pasting sheet-like materials.
すなわち、本発明の方法によればビニルモノマーが連続
相となり、その中に水とセメントが分散しているセメン
ト含有讐/O型エマルジ3ンに、上記補強繊維が分散し
ている状態の押出成形原材料を押出成形するのである。That is, according to the method of the present invention, the reinforcing fibers are extruded into a cement-containing O-type emulsion in which the vinyl monomer becomes a continuous phase and water and cement are dispersed therein. The raw materials are extruded.
この原材料組成物の逆エマルジョンの連続相、すなわち
、マトリックスが油性のビニルモノマーであることから
、従来のセメント−水溶性高分子化合物よりなる原材料
組成物と比較して、合成樹脂系の補強繊維との親和性が
著しく高いので、補強繊維の分散性、補強効果及び原材
料の流動性において優れた効果を示すものである。Since the continuous phase of the inverse emulsion of this raw material composition, that is, the matrix, is an oil-based vinyl monomer, compared to the conventional raw material composition made of cement-water-soluble polymer compound, it is difficult to use synthetic resin-based reinforcing fibers. Because of its extremely high affinity for reinforcing fibers, it exhibits excellent effects on the dispersibility of reinforcing fibers, the reinforcing effect, and the fluidity of raw materials.
更に、本発明のセメント含有W/O型エマルジョンは貰
いチクソトロピー性を有しているので大きな外力がかか
ると流動するが、静置すると形状が崩れないため小さい
孔を多数有する押出成形物を容易に得ることができる。Furthermore, since the cement-containing W/O emulsion of the present invention has thixotropic properties, it will flow when a large external force is applied, but it will not lose its shape when left standing, so it can be easily made into extrudates with many small pores. Obtainable.
本発明において、セメント含有W/O型エマルジ5ンは
、セメント/O0重量部に対して水40〜500重量部
、好ましくは50〜200重量部からなるセメントスラ
リーに非水溶性ビニルモノマーと逆乳化剤、重合開始剤
とからなるビニルモノマー溶液を1〜20重量%好まし
くは2〜/O重量%を加えて市販のミキサーにて0.5
〜5分間撹拌して得られる。前記セメント含有讐/O型
エマルジョンは油性の柔らかい粘土状であるので合成繊
維とのなじみが非常によく前処理を施すことなく、単に
混入するだけで均一に分散させることができる。In the present invention, the cement-containing W/O emulsion is prepared by adding a water-insoluble vinyl monomer and an inverse emulsifier to a cement slurry consisting of 40 to 500 parts by weight, preferably 50 to 200 parts by weight of water based on parts by weight of cement/O0. , a vinyl monomer solution consisting of a polymerization initiator is added in an amount of 1 to 20% by weight, preferably 2 to 0.0% by weight, and 0.5% by weight is added using a commercially available mixer.
Obtained by stirring for ~5 minutes. Since the cement-containing O/O type emulsion is in the form of oil-based soft clay, it is very compatible with synthetic fibers and can be uniformly dispersed simply by mixing them without any pretreatment.
本発明で使用するセメントとしては、ポルトランドセメ
ント、高炉セメント、フライアッシュセメント、シリカ
セメント、あるいは珪酸化合物、カルシウム化合物等が
挙げられる。Examples of the cement used in the present invention include Portland cement, blast furnace cement, fly ash cement, silica cement, silicic acid compounds, and calcium compounds.
補強繊維としては、ポリプロピレン、ポリエステル、ビ
ニロン、ナイロン、アクリル、アラミド繊維が用いられ
る。前記補強繊維は、補強効果、分散性の点からアスペ
クト比が/O0〜2000、長さが2〜20II1mの
ものが好ましい。As reinforcing fibers, polypropylene, polyester, vinylon, nylon, acrylic, and aramid fibers are used. The reinforcing fibers preferably have an aspect ratio of /O0 to 2000 and a length of 2 to 20II1 m from the viewpoint of reinforcing effect and dispersibility.
ビニルモノマーはセメント含有W/O型エマルジョンを
製造する際合成繊維となじみやすくするため常温で液体
であって水に難溶性のものが好」しい。The vinyl monomer is preferably liquid at room temperature and poorly soluble in water in order to make it compatible with synthetic fibers when producing a cement-containing W/O emulsion.
例えば、スチレン、αメチルスチレン、アクリル酸エス
テル、メタクリル酸エステル、アクリロニトリル、ジビ
ニルベンゼン、アルキレンゲルコールのアクリル酸また
はメタクリル酸エステル、多価アルコールのアクリル酸
またはメタクリル酸エステル等が挙げられる。これらは
単独で用いても良いし、二種以上混合して使用しても良
い。上記とニルモノマーの中では特にスチしンを主成分
とするとニルモノマー混合物を使用するのが好ましい。Examples include styrene, α-methylstyrene, acrylic ester, methacrylic ester, acrylonitrile, divinylbenzene, acrylic or methacrylic ester of alkylene gelcol, acrylic or methacrylic ester of polyhydric alcohol, and the like. These may be used alone or in combination of two or more. Among the above-mentioned and nil monomers, it is particularly preferable to use a mixture of nil monomers, especially when the main component is styrene.
又成形物の強度や重合特性を高める目的で用いられる多
価アルコールのジメタクリレート、又はトリメタクリレ
ート化合物としては例えばエチレンゲルコールジメタク
リレート、トリメチロールプロパントリメタクリし一ト
等のジビニル化合物やトリビニル化合物を併用すること
が好ましい。In addition, dimethacrylate or trimethacrylate compounds of polyhydric alcohols used for the purpose of increasing the strength and polymerization properties of molded products include divinyl and trivinyl compounds such as ethylene gelcol dimethacrylate and trimethylolpropane trimethacrylate. It is preferable to use them together.
ビニルモノマーには、成形後の養生硬化反応を促進する
ために重合触媒を混入するが、重合触媒は一般的なラジ
カル形成剤又はレドックス触媒を通常の処方に従って使
用する。A polymerization catalyst is mixed into the vinyl monomer in order to promote curing reaction after molding, and a general radical forming agent or redox catalyst is used as the polymerization catalyst according to a usual recipe.
セメント含有W/O型エマルジ1ンを形成させるための
逆乳化剤は、HLB価が3〜6の非イオン性界面活性剤
をビニルモノマーに対して3〜50重量%溶解して使用
するが、別々に加えてもセメント含有W/O型エマルジ
ョンは形成される。本発明では、使用するHLB価が3
〜6の非イオン界面活性剤としては、例えばソルビタン
モノオレート、グリセロールモノステアレート、ソルビ
タンモノオレエート、ジエチレングリコールモノステア
レート、ソルビタンモノステアレート、ジグリセロール
モノオレエート、アルキレングリコールの無水マレイン
酸付加物等が挙げられる。これらは単独で用いてもよい
し二種以上混合して用いてもよい。単独で用いる場合は
ソルビタンモノオレート、ジグリセロールモノオレート
が好ましい。その他必要に応じてパーライト、バーミキ
ュライト、シラスバルーン、ガラスバルーン、合成樹脂
発泡体などを軽量骨材として混入してもよい。The inverse emulsifier for forming a cement-containing W/O emulsion is a nonionic surfactant with an HLB value of 3 to 6 dissolved in a proportion of 3 to 50% by weight relative to the vinyl monomer. A cement-containing W/O emulsion is also formed. In the present invention, the HLB value used is 3.
Examples of the nonionic surfactants 6 to 6 include sorbitan monooleate, glycerol monostearate, sorbitan monooleate, diethylene glycol monostearate, sorbitan monostearate, diglycerol monooleate, and maleic anhydride adducts of alkylene glycol. etc. These may be used alone or in combination of two or more. When used alone, sorbitan monooleate and diglycerol monooleate are preferred. In addition, pearlite, vermiculite, shirasu balloons, glass balloons, synthetic resin foams, etc. may be mixed as lightweight aggregates as necessary.
以上述べた補強繊維を含むセメント含有!//O型エマ
ルジ5ンは、出口部に中空部を形成する中子を有する多
孔中空板成形用ダイスを備えた押出成形機にて成形され
る。本発明でいう中空板とは、押出方向に対して平行に
多数の柱状の中空孔が形成された板状物である。押出成
形された多孔中空成形板は自然養生、蒸気養生、オート
クレーブ養生にてビニルモノマーの重合とセメントの水
和反応を進行させ、硬化させた後乾燥させる。Contains cement including the reinforcing fibers mentioned above! //O-type emulsion 5 is molded using an extrusion molding machine equipped with a die for molding a porous hollow plate having a core that forms a hollow portion at the outlet. The hollow plate referred to in the present invention is a plate-like object in which a large number of columnar hollow holes are formed in parallel to the extrusion direction. The extruded porous hollow molded plate is cured by natural curing, steam curing, and autoclave curing to advance the polymerization of vinyl monomer and the hydration reaction of cement, and is then dried after hardening.
然る後その表裏面に接着剤を介して板状物又はシート状
物を貼着する。Thereafter, a plate-like object or a sheet-like object is attached to the front and back surfaces using an adhesive.
前記板状物又はシート状物としては、合板、パーティク
ルボード、ファイバーボード等の木質系、スチレン、ポ
リエステル、エポキシ、塩化ビニル、メラミン、フェノ
ール樹脂等のプラスチック系、鉄、アルミニウム、ステ
ンレス等の金属系の板又はシートの他織布、不織布が用
いられる。The plate-like or sheet-like materials include wood-based materials such as plywood, particle board, and fiberboard, plastic-based materials such as styrene, polyester, epoxy, vinyl chloride, melamine, and phenolic resin, and metal-based materials such as iron, aluminum, and stainless steel. In addition to plates or sheets, woven fabrics and non-woven fabrics are used.
これらの板状物又はシート状物は意匠性を付与するため
に着色、絵柄模様を印刷したものが好ましい。These plate-like products or sheet-like products are preferably colored or printed with patterns to give them a design.
尚、これら板状物又はシート状物を多孔中空板に貼着す
る際の接着剤については特に制限はないが、ゴム系、エ
ポキシ系、酢酸ビニル系、フェノール系の接着剤が用い
られる。There are no particular restrictions on the adhesive used to adhere these plate-like objects or sheet-like objects to the porous hollow plate, but rubber-based, epoxy-based, vinyl acetate-based, and phenol-based adhesives can be used.
上記多孔中空板に含まれているビニルポリマーは上記接
着剤とのなじみがよいため接着性の向上に寄与するもの
である。The vinyl polymer contained in the porous hollow plate has good compatibility with the adhesive and thus contributes to improved adhesiveness.
[実施例] 以下実施例にて本発明の詳細な説明する。[Example] The present invention will be explained in detail in Examples below.
実施例1
連続ニーダ−に、ポルトランドセメントを毎時307.
8Kg、水を275.4Kg1ビニルモノマー溶液を毎
時16゜0Kg、アスペクト比が333、長さが6mm
のアクリル繊維を毎時5Kg連続的に供給し、補強繊維
がよく分散したセメント含有W/O型エマルシリンを得
た。たたし、とニルモノマー溶液はスチレンモノマー6
9重量部、ソルビタンモノオレート25重量部、トリメ
チロールプ0パントリメタクリレート5重量部、ベンゾ
イルパーオキサイド1重量部の混合物であった。得られ
たセメント含有W/O型エマルジョンは、やわらかな粘
土状で水には溶解しなかった。このセメント含有V/O
型エマルジ9ン組成物を中空成形用ダイスを備えた押出
機に連続的に供給し、0.3Kg/cm2の押出圧で厚
さ30mm、輻455mm、中空率25%の多孔中空板
を連続押出成形した。得られた押出成形板を50℃で1
7時間、90℃で24時間蒸気養生して硬化させた後乾
燥して比重が0.75の多孔中空板を得た。この多孔中
空成形板は乾燥後も押出成形時と同じ形状を維持してお
り、変形、形崩れは認められなかった。この多孔中空成
形板のJIS A1408に基づく曲げ破壊荷重は30
mm厚で330Kgであった。Example 1 Portland cement was fed into a continuous kneader at a rate of 307.
8Kg, 275.4Kg of water, 16°0Kg of vinyl monomer solution per hour, aspect ratio 333, length 6mm
5 kg of acrylic fibers were continuously supplied per hour to obtain cement-containing W/O type emulsion in which reinforcing fibers were well dispersed. The styrene monomer solution is styrene monomer 6.
It was a mixture of 9 parts by weight of sorbitan monooleate, 25 parts by weight of trimethylolpantrimethacrylate, and 1 part by weight of benzoyl peroxide. The obtained cement-containing W/O emulsion was soft clay-like and did not dissolve in water. This cement containing V/O
The emulsion composition was continuously fed into an extruder equipped with a die for blow molding, and a porous hollow plate with a thickness of 30 mm, a diameter of 455 mm, and a hollow ratio of 25% was continuously extruded at an extrusion pressure of 0.3 Kg/cm2. Molded. The obtained extrusion molded plate was heated at 50°C for 1
After being cured with steam for 7 hours and 24 hours at 90°C, it was dried to obtain a porous hollow plate having a specific gravity of 0.75. This porous hollow molded plate maintained the same shape as when it was extruded even after drying, and no deformation or deformation was observed. The bending failure load of this porous hollow molded plate is 30 based on JIS A1408.
It was 330 kg in mm thickness.
この多孔中空成形板の表裏面に厚さ0.6mmのメラミ
ン焼付鉄板をエポキシ系接着剤で貼着した。得られた多
孔中空複合板は前記鉄板が非常に強固に接着しているの
で強度及び意匠性に優れたものであった。Melamine baked iron plates having a thickness of 0.6 mm were adhered to the front and back surfaces of this porous hollow molded plate using an epoxy adhesive. The obtained porous hollow composite plate had excellent strength and design because the iron plate was bonded very firmly.
実施例2
連続ニーダ−に高炉セメントを毎時453.6Kg、水
を毎時226.8Kg、ビニルモノマー溶液を毎時16
.0Kg。Example 2 453.6 kg of blast furnace cement per hour, 226.8 kg of water per hour, and 16 kg of vinyl monomer solution per hour in a continuous kneader
.. 0Kg.
アスペクト比が/O00、長さが12n+mのビニロン
繊維を毎時7.0Kg連続的に供給し、補強繊維がよく
分散したセメント含有W/O型エマルジョンを得た。た
だしビニルモノマー溶液はスチレンモノマー74重量部
、エチレングリコールジメタクリレート5重量部、ジグ
リヤロールモノオレー820重量部、t−ブチルパーオ
キシベンゾエート1重量部の混合物であった。得られた
セメント含有V/O型エマルジョンはやわらかい粘土状
で水には溶解しなかった。このセメント含有W/O型エ
マルジョン組成物を中空成形用のダイスを備えた押出機
に連続的に提供し0.5Kg/c+a2の押出圧で厚す
18m+++、1g455mm、中空率30$ノ中空板
を連続成形した。得られた押出成形板を50℃で17時
間、90℃で24時間蒸気養生して硬化させた後乾燥し
て比重が1.1の多孔中空成形板を得た。この多孔中空
成形板は乾燥後も押出成形時と同じ形状を維持しており
、変形、形崩れは認められなかった。Vinylon fibers having an aspect ratio of /O00 and a length of 12n+m were continuously fed at 7.0 kg per hour to obtain a cement-containing W/O emulsion in which reinforcing fibers were well dispersed. However, the vinyl monomer solution was a mixture of 74 parts by weight of styrene monomer, 5 parts by weight of ethylene glycol dimethacrylate, 820 parts by weight of diglyarol monoolet, and 1 part by weight of t-butyl peroxybenzoate. The obtained cement-containing V/O emulsion was soft clay-like and did not dissolve in water. This cement-containing W/O emulsion composition was continuously supplied to an extruder equipped with a die for blow molding, and a hollow plate with a thickness of 18 m+++, 1 g of 455 mm, and a hollow ratio of 30 $ was produced using an extrusion pressure of 0.5 kg/c+a2. Continuously molded. The obtained extrusion-molded plate was cured by steam curing at 50°C for 17 hours and at 90°C for 24 hours, and then dried to obtain a porous hollow-molded plate having a specific gravity of 1.1. This porous hollow molded plate maintained the same shape as when it was extruded even after drying, and no deformation or deformation was observed.
得られた多孔中空成形板のJIS A1408に基づく
曲げ破壊荷重は180Kgであった。The bending failure load of the obtained porous hollow-formed plate based on JIS A1408 was 180 kg.
この多孔中空板の表面に織布をゴム系接着剤で貼着した
。A woven fabric was attached to the surface of this porous hollow plate using a rubber adhesive.
得られた多孔中空複合板は織布が強固に接着した意匠性
に優れたものであった。The resulting porous hollow composite board had excellent design with the woven fabric firmly adhered to it.
実施例3
連続ニーダ−にポルトランドセメントを毎時162゜0
kg、水を324.0Kg、とニルモノマー溶液を毎時
16.0にg1アスペクト比が500で長さが6111
のアラミド繊維を毎時/O.0Kg連続的に供給し、補
強繊維がよく分散したセメント含有W/O型エマルジョ
ンを得た。ただし、とニルモノマー溶液はスチレンモノ
マー64重量部、ソルビタンモノオレート30重量部、
トリメチロールプロパントリメタクリレート5重量部、
t−ブチルパーオキシイソプロビルカーボネート1重量
部の混合物であフた。得られたセメント含有w/O型エ
マルジ5ンはやわらかい粘土状で、水には溶解しなかっ
た。このセメント含有V/O型エマルジョン組成物を中
空板成形用のダイスを備えた押出機に連続的に供給し0
.2Kg/cm2の押出圧で厚さ35!ll11.、輻
455■、中空率20%の中空板を連続押出成形した。Example 3 Portland cement was fed into a continuous kneader at 162°/hour.
kg, 324.0 kg of water, and 16.0 kg of nil monomer solution per hour, g1 aspect ratio is 500, and length is 6111.
of aramid fiber per hour/O. 0 kg was continuously supplied to obtain a cement-containing W/O emulsion in which reinforcing fibers were well dispersed. However, the monomer solution contains 64 parts by weight of styrene monomer, 30 parts by weight of sorbitan monooleate,
5 parts by weight of trimethylolpropane trimethacrylate,
A mixture of 1 part by weight of t-butylperoxyisopropyl carbonate was added. The obtained cement-containing w/O type emulsion was soft clay-like and did not dissolve in water. This cement-containing V/O emulsion composition was continuously fed into an extruder equipped with a die for forming hollow plates.
.. Thickness 35 with extrusion pressure of 2Kg/cm2! ll11. A hollow plate having a diameter of 455 cm and a hollowness ratio of 20% was continuously extruded.
得られた押出成形板は60℃で8時間蒸気養生した後1
35℃で18M間オートクレーブにて蒸気養生して硬化
した後乾燥して比重が0.52の多孔中空成形板を得た
。The obtained extrusion molded plate was steam-cured at 60°C for 8 hours and then
The material was steam-cured in an autoclave for 18M at 35° C., cured, and then dried to obtain a porous hollow-molded plate having a specific gravity of 0.52.
この多孔中空成形板は乾燥後も押出成形時と同じ形状を
維持しており、変形、形崩れは認められなかった。This porous hollow molded plate maintained the same shape as when it was extruded even after drying, and no deformation or deformation was observed.
得られた多孔中空板のJIS A1408に基づく曲げ
破壊荷重は35mm厚で380Kgであった。The bending fracture load of the obtained porous hollow plate based on JIS A1408 was 380 kg at a thickness of 35 mm.
この多孔中空板の表裏面に厚さ5.5mmの難燃シナ合
板を酢酸ビニル系接着剤で貼着した。Flame-retardant Chinese plywood with a thickness of 5.5 mm was adhered to the front and back surfaces of this porous hollow board using a vinyl acetate adhesive.
合板が強固に接着した意匠性に優れた多孔中空成形板が
得られた。A porous hollow-molded board with excellent design to which plywood was firmly adhered was obtained.
実施例4
スチレンモノマー54重量部、アクリロニトリル/O重
量部、平均分子量2000のポリアルキレングリコール
の無水マレイン酸付加物30重量部、エチレングリコー
ルジメタクリレート5重量部、ベンゾイルパーオキサイ
ド1重量部、ポルトランドセメント400重量部、水8
00重量部、シラスバルーン20重量部、ポリプロピレ
ン繊維13重量部を双腕ニーダ−にて混合撹拌して、補
強繊維のよく分散したセメント含有V/O型エマルジッ
ンを得た。このセメント含有讐/O型エマルジ5ンは水
には溶解しなかった。このセメント含有W/O型エマル
ジ!ン組成物を中空成形用ダイスを備えた押出機にて0
.7にg/c12の押出圧で押出成形して、厚さ35m
g+、輻455mm、中空率20Xの多孔中空板を成形
した。この中空板を常温で28日開放置し、硬化乾燥し
たものの比重は0.45であった。この多孔中空板は押
出成形時と同一形状を維持しており、変形、形崩れはな
くシラスバルーンの破壊も認められなかった。Example 4 54 parts by weight of styrene monomer, parts by weight of acrylonitrile/O, 30 parts by weight of maleic anhydride adduct of polyalkylene glycol with an average molecular weight of 2000, 5 parts by weight of ethylene glycol dimethacrylate, 1 part by weight of benzoyl peroxide, 400 parts by weight of Portland cement Parts by weight, 8 parts water
00 parts by weight, 20 parts by weight of Shirasu balloons, and 13 parts by weight of polypropylene fibers were mixed and stirred in a double-arm kneader to obtain a cement-containing V/O emulsion in which reinforcing fibers were well dispersed. This cement-containing O/O emulsion did not dissolve in water. This cement-containing W/O type emulsion! The composition was heated to zero in an extruder equipped with a blow molding die.
.. 7 to extrusion molding at an extrusion pressure of 12 g/c to a thickness of 35 m.
A porous hollow plate with g+, radius 455 mm, and hollowness ratio 20X was molded. This hollow plate was left open at room temperature for 28 days, and after hardening and drying, the specific gravity was 0.45. This porous hollow plate maintained the same shape as when it was extruded, and there was no deformation or loss of shape, and no destruction of the shirasu balloon was observed.
得られた多孔中空板のJIS A1408に基づく曲げ
破壊荷重は35m+++厚で350Kgであった。The bending failure load of the obtained porous hollow plate based on JIS A1408 was 350 kg at a thickness of 35 m+++.
この多孔中空板の表裏面にメラミン板をエポキシ接着剤
で貼着したものは、強固に接着しているので優れた堅牢
性を示した。Melamine plates were attached to the front and back surfaces of this porous hollow plate using an epoxy adhesive, and the bond was strong and showed excellent robustness.
比較例1
ポルトランドセメント60重量部、けい砂12重量部、
石綿12重量部、シラスバルーン20重量部、メチルセ
ルロース1重量部を混合し、石綿をよく分散させた後、
水を60重量部加え、粘土状とし、成形用ダイスを備え
た押出機にて3にg/c■2の押出圧にて押出成形して
厚さが18層1、輻455層層、の中実板を速続押出成
形した。得られた中実板を実施例1と同様にして硬化乾
燥し、その表裏面に厚さ1mmのメラミン板をエポキシ
接着剤で貼着した。Comparative Example 1 60 parts by weight of Portland cement, 12 parts by weight of silica sand,
After mixing 12 parts by weight of asbestos, 20 parts by weight of Shirasu balloons, and 1 part by weight of methyl cellulose and dispersing the asbestos well,
Add 60 parts by weight of water to make it clay-like, and extrude it using an extruder equipped with a molding die at an extrusion pressure of 3g/cm2 to a thickness of 18 layers and a diameter of 455 layers. A solid plate was formed by rapid extrusion. The obtained solid board was cured and dried in the same manner as in Example 1, and melamine boards with a thickness of 1 mm were attached to the front and back surfaces using an epoxy adhesive.
このメラミン板を貼着した前記中実板は若干のたわみで
メラミン板が剥がれ優れた堅牢性は認められなかった。The solid board to which this melamine board was attached was not found to have excellent robustness because the melamine board peeled off due to slight bending.
[発明の効果]
以上述べた如く、本発明の方法により得られた多孔中空
複合板は、セメント含有W/O型エマルジョンに含まれ
るとニルモノマーが補強用合成繊維となじみがよいため
、高い補強効果が得られ、セメント複合板の非アスベス
ト化が達成されるものである。[Effects of the Invention] As described above, the porous hollow composite board obtained by the method of the present invention has a high reinforcing effect because the nyl monomer is compatible with the reinforcing synthetic fiber when included in the cement-containing W/O emulsion. As a result, asbestos-free cement composite boards can be achieved.
更に本発明の多孔中空複合板は、前記ビニルモノマーが
接着剤とのなじみがよいため多孔中空複合板の表裏面に
貼着する板状物又はシート状物と強固に接着するので、
耐折曲性が向上し、長尺物の生産が容易になるものであ
る。Furthermore, the porous hollow composite board of the present invention has good compatibility with adhesives, so that it firmly adheres to plate-like objects or sheet-like objects attached to the front and back surfaces of the porous hollow composite board.
This improves bending resistance and facilitates the production of long products.
Claims (5)
ルモノマーと水と合成繊維から得られる補強繊維が分散
されたセメント含有W/O型エマルジョンの多孔中空押
出成形板を養生硬化した後、乾燥し、表裏面に板状物又
はシート状物を貼着する事を特徴とする多孔中空複合板
の製造方法。(1) After curing and curing a porous hollow extrusion molded plate of a cement-containing W/O type emulsion in which reinforcing fibers obtained from a water-insoluble vinyl monomer containing a polymerization initiator and an inverse emulsifier, water, and synthetic fibers are dispersed. A method for producing a porous hollow composite board, which comprises drying and pasting a plate-like material or a sheet-like material on the front and back surfaces.
板である請求項1記載の多孔中空複合板の製造方法。(2) The method for producing a porous hollow composite board according to claim 1, wherein the plate-like material or sheet-like material to be attached to the front and back surfaces is a wood-based board.
チック板又はプラスチックシートである請求項1記載の
多孔中空複合板の製造方法。(3) The method for producing a porous hollow composite plate according to claim 1, wherein the plate-like object or sheet-like object to be attached to the front and back surfaces is a plastic plate or a plastic sheet.
又は金属シートである請求項1記載の多孔中空複合板の
製造方法。(4) The method for producing a porous hollow composite plate according to claim 1, wherein the plate-like object or sheet-like object to be attached to the front and back surfaces is a metal plate or a metal sheet.
又は不織布である請求項1記載の多孔中空複合板の製造
方法。(5) The method for producing a porous hollow composite board according to claim 1, wherein the plate-like material or sheet-like material to be adhered to the front and back surfaces is a woven fabric or a non-woven fabric.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20268690A JPH0485023A (en) | 1990-07-30 | 1990-07-30 | Manufacture porous hollow composite sheet |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20268690A JPH0485023A (en) | 1990-07-30 | 1990-07-30 | Manufacture porous hollow composite sheet |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0485023A true JPH0485023A (en) | 1992-03-18 |
Family
ID=16461477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20268690A Pending JPH0485023A (en) | 1990-07-30 | 1990-07-30 | Manufacture porous hollow composite sheet |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0485023A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006150825A (en) * | 2004-11-30 | 2006-06-15 | Kubota Matsushitadenko Exterior Works Ltd | Manufacturing method of decorative sheet-pasted inorganic panel |
JP2006150824A (en) * | 2004-11-30 | 2006-06-15 | Kubota Matsushitadenko Exterior Works Ltd | Manufacturing method of inorganic panel with backing sheet |
CN102152375A (en) * | 2011-03-01 | 2011-08-17 | 南京林业大学 | Hollow density board and extruding manufacturing method |
-
1990
- 1990-07-30 JP JP20268690A patent/JPH0485023A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006150825A (en) * | 2004-11-30 | 2006-06-15 | Kubota Matsushitadenko Exterior Works Ltd | Manufacturing method of decorative sheet-pasted inorganic panel |
JP2006150824A (en) * | 2004-11-30 | 2006-06-15 | Kubota Matsushitadenko Exterior Works Ltd | Manufacturing method of inorganic panel with backing sheet |
JP4585294B2 (en) * | 2004-11-30 | 2010-11-24 | クボタ松下電工外装株式会社 | Manufacturing method of inorganic board with backing sheet |
JP4598500B2 (en) * | 2004-11-30 | 2010-12-15 | ケイミュー株式会社 | Manufacturing method of inorganic sheet with decorative sheet |
CN102152375A (en) * | 2011-03-01 | 2011-08-17 | 南京林业大学 | Hollow density board and extruding manufacturing method |
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