JP4559716B2 - Cement composite - Google Patents
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- JP4559716B2 JP4559716B2 JP2003301242A JP2003301242A JP4559716B2 JP 4559716 B2 JP4559716 B2 JP 4559716B2 JP 2003301242 A JP2003301242 A JP 2003301242A JP 2003301242 A JP2003301242 A JP 2003301242A JP 4559716 B2 JP4559716 B2 JP 4559716B2
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本発明は、セメント、水、油性物質及び乳化剤からなるセメント含有Ｗ／Ｏ型エマルジョン組成物を成形して得られるセメント複合材に関するものである。 The present invention relates to a cement composite obtained by molding a cement-containing W / O emulsion composition comprising cement, water, an oily substance and an emulsifier.
押出成形等で形成されるセメント系成形品は、耐候性、耐火性に優れ、また製造コストも低いことから、建築材料として広く利用されている。 Cement-based molded articles formed by extrusion molding or the like are widely used as building materials because they are excellent in weather resistance and fire resistance and have low production costs.
従来、セメント系成形品を製造する有効な方法として、セメント、水、及び油性物質からなるセメント含有Ｗ／Ｏエマルジョン組成物を利用する方法が提案されている（特許文献１，２参照）。このセメント含有Ｗ／Ｏエマルジョン組成物は、成形時の保形性に優れており、また、水／セメント比を変化させることでセメント系成形品の比重を自由にコントロールすることができるという特徴を有している。 Conventionally, as an effective method for producing a cement-based molded article, a method using a cement-containing W / O emulsion composition composed of cement, water, and an oily substance has been proposed (see Patent Documents 1 and 2). This cement-containing W / O emulsion composition has excellent shape retention during molding, and the specific gravity of the cement-based molded product can be freely controlled by changing the water / cement ratio. Have.
更に、このようにして得られるセメント系成形品は、微細でかつ均一な発泡構造を有しているため、表面平滑性、鋸引き性や、釘打ち性等の加工性、或いはネジ保持力に優れた性質を有していることが知られている。 Furthermore, since the cement-based molded product thus obtained has a fine and uniform foamed structure, surface smoothness, sawing property, processability such as nailability, and screw holding power are improved. It is known to have excellent properties.
しかしながら、セメント含有Ｗ／Ｏエマルジョン組成物から形成されるセメント成形板を外装材として利用するには、耐凍害性や曲げ強度が不充分であり、或いは所望の性能を得ることが困難であった。 However, in order to use a cement molded board formed from a cement-containing W / O emulsion composition as an exterior material, the frost damage resistance and bending strength are insufficient, or it is difficult to obtain desired performance. .
例えば特許文献１には、成形品の細孔径や細孔の独立性を制御して耐凍害性を向上させる技術が開示されているが、製造条件の管理が非常に厳しく、大量生産が困難なものであった。 For example, Patent Document 1 discloses a technique for improving the frost damage resistance by controlling the pore diameter and pore independence of a molded product, but the management of manufacturing conditions is very strict and mass production is difficult. It was a thing.
このような耐凍害性や曲げ強度等を向上するためには、セメント含有Ｗ／Ｏエマルジョン組成物中に補強繊維を含有させることが考えられるが、一般的に用いられる補強繊維であるパルプは、吸水性が高く、このため組成物中の水分を吸収してＷ／Ｏエマルジョン構造を破壊してしまうおそれがあった。
本発明は上記の点に鑑みて為されたものであり、セメント、水、油性物質及び乳化剤からなるセメント含有Ｗ／Ｏ型エマルジョン組成物を成形して得られ、且つ耐凍害性と曲げ強度とに優れ、特に外装材として好適に用いることができるセメント複合材を提供することを目的とするものである。 The present invention has been made in view of the above points, and is obtained by molding a cement-containing W / O emulsion composition composed of cement, water, an oily substance, and an emulsifier, and has frost resistance and bending strength. It is an object of the present invention to provide a cement composite material that is excellent in performance and particularly suitable for use as an exterior material.
本発明に係るセメント複合材は、セメント、水、油性物質及び乳化剤からなるセメント含有Ｗ／Ｏ型エマルジョン組成物を成形して得られるセメント複合材において、前記セメント含有Ｗ／Ｏ型エマルジョン組成物中に補強繊維を混合し、補強繊維として解繊の際にシラン系撥水処理剤を添加して撥水処理を施したパルプを用いることを特徴とするものである。これにより、セメント含有Ｗ／Ｏ型エマルジョン組成物中に補強繊維としてパルプを含有させると共にこのパルプの吸水によりセメント含有Ｗ／Ｏ型エマルジョン組成物中のＷ／Ｏエマルジョン構造が破壊されることを防ぐことができる。またシラン系撥水剤は、撥水効果が大きく、またセメントの硬化反応に悪影響を及ぼすことがなく、またパルプとの吸着性にも優れているものである。 The cement composite according to the present invention is a cement composite obtained by molding a cement-containing W / O emulsion composition comprising cement, water, an oily substance, and an emulsifier. The fiber is mixed with a reinforcing fiber, and a pulp which has been subjected to water repellent treatment by adding a silane-based water repellent treatment agent at the time of defibration is used as the reinforcing fiber. Thereby, pulp is contained as a reinforcing fiber in the cement-containing W / O emulsion composition, and the W / O emulsion structure in the cement-containing W / O emulsion composition is prevented from being destroyed by water absorption of the pulp. be able to. Silane-based water repellents have a large water repellent effect, do not adversely affect the curing reaction of cement, and are excellent in adsorbability with pulp.
本発明に係るセメント複合材は、上記のような補強繊維を含有すると共に補強繊維の吸水によるＷ／Ｏエマルジョン構造の破壊が防止されたセメント含有Ｗ／Ｏ型エマルジョン組成物にて形成されることから、良好な多孔質性を有すると共に、優れた耐凍害性と曲げ強度とを有し、特に外装材として好適に用いることが可能となるものである。 The cement composite according to the present invention is formed of a cement-containing W / O emulsion composition containing the reinforcing fibers as described above and preventing destruction of the W / O emulsion structure due to water absorption of the reinforcing fibers. Therefore, it has good porosity and excellent frost resistance and bending strength, and can be suitably used particularly as an exterior material.
本発明でいう、セメント複合材は、少なくともセメント、水及び油性物質を原料とするＷ／Ｏエマルジョン組成物を成形して得られるものであって、主成分が無機質からなる多孔性の成形品を意味しており、無機質材以外に少量の各種成分が添加、混合されていたり、合成樹脂で無機質材が結合されたものであっても何ら差し支えない。 The cement composite material referred to in the present invention is obtained by molding a W / O emulsion composition using at least cement, water and an oily material as raw materials, and is a porous molded article whose main component is inorganic. This means that a small amount of various components in addition to the inorganic material may be added and mixed, or even if the inorganic material is combined with a synthetic resin.
セメントとしては、ポルトランドセメント、フライアッシュ、高炉スラグ等を挙げることができる。 Examples of the cement include Portland cement, fly ash, and blast furnace slag.
油性物質としては、水とＷ／Ｏエマルジョンを形成しうるものであれば、特に制限はなく、通常疎水性の液状物質が利用されるが、例えば、トルエン、キシレン、灯油、スチレン、ジビニルベンゼン、メチルメタクリレート、トリメチロールプロパントリメタクリレート、不飽和ポリエステル樹脂等が挙げられる。特に、油性物質として、スチレン、ジビニルベンゼン、メチルメタクリレート、トリメチロールプロパントリメタクリレート、不飽和ポリエステル樹脂等の重合性二重結合を有するもの（ビニル単量体）を使用すれば、これらが重合したポリマーがマトリックスを形成して得られるセメント複合材の物理的、機械的性質を向上すると共に、後述するように得られるセメント複合材中の独立気孔中に水が浸入しにくくなり、吸水率を低下させることができるので好ましい。また重合性二重結合を有する油性物質を使用する場合には、油性物質の重合を促進するために、有機過酸化物等の重合開始剤を併用することが望ましい。 The oily substance is not particularly limited as long as it can form a W / O emulsion with water, and usually a hydrophobic liquid substance is used. For example, toluene, xylene, kerosene, styrene, divinylbenzene, Examples include methyl methacrylate, trimethylolpropane trimethacrylate, and unsaturated polyester resin. In particular, if an oily substance having a polymerizable double bond (vinyl monomer) such as styrene, divinylbenzene, methyl methacrylate, trimethylolpropane trimethacrylate, or an unsaturated polyester resin is used, a polymer obtained by polymerizing them. Improves the physical and mechanical properties of the cement composite obtained by forming a matrix, and makes it difficult for water to enter the independent pores in the cement composite obtained as described later, thereby reducing the water absorption rate. This is preferable. When an oily substance having a polymerizable double bond is used, it is desirable to use a polymerization initiator such as an organic peroxide in combination in order to accelerate the polymerization of the oily substance.
組成物中の油性物質の含有量は、組成物中に水とのＷ／Ｏエマルジョンを形成でき、且つ得られるセメント複合材に所望の特性が付与されるように、適宜調整されるものであるが、例えば組成物中におけるセメント及び水（骨材を加える場合には更に骨材）の含有量の総量に対して５〜１０体積％の範囲であることが好ましい。 The content of the oily substance in the composition is appropriately adjusted so that a W / O emulsion with water can be formed in the composition and desired characteristics are imparted to the resulting cement composite. However, it is preferable that it is the range of 5-10 volume% with respect to the total amount of the content of cement and water (in the case of adding an aggregate, further aggregate) in a composition, for example.
また、本発明においては、Ｗ／Ｏエマルジョン組成物中には、撥水処理が施された補強繊維が含有される。補強繊維としては、適宜のものが挙げられるが、安価な有機繊維が好ましく、特にパルプを用いることが好ましい。尚、撥水処理は、パルプ繊維のような親水性の繊維に特に有効に作用するが、アクリル繊維のような親油性の繊維においても有効に作用する。 In the present invention, the W / O emulsion composition contains a reinforcing fiber that has been subjected to a water repellent treatment. Examples of the reinforcing fiber include appropriate ones, but inexpensive organic fibers are preferable, and pulp is particularly preferable. The water repellent treatment is particularly effective for hydrophilic fibers such as pulp fibers, but is also effective for lipophilic fibers such as acrylic fibers.
また組成物中の補強繊維の含有量は、形成されるセメント複合材に所望の耐凍害性と曲げ強度とを付与することができるように適宜調整されるが、好ましくは組成物中におけるセメント及び水（骨材を加える場合には更に骨材）の含有量の総量に対して０．１〜８体積％の範囲とするものである。 Further, the content of the reinforcing fiber in the composition is appropriately adjusted so as to impart desired frost resistance and bending strength to the formed cement composite, but preferably the cement and the cement in the composition The content is in the range of 0.1 to 8% by volume with respect to the total content of water (or aggregate when adding aggregate).
このとき、補強繊維の寸法は適宜設定されるが、好ましくは繊維長が１０ｍｍ以下のものを用いる。 At this time, the dimensions of the reinforcing fibers are appropriately set, but those having a fiber length of 10 mm or less are preferably used.
また補強繊維はパルプに限られるものではなく、例えばアクリル繊維、ビニロン繊維、ポリプロピレン繊維、アラミド繊維等の合成繊維や炭素繊維、ガラス繊維等の補強繊維を併用することも勿論可能である。特に補強繊維を併用した場合、機械的強度が更に向上するので、好ましい。 Further, the reinforcing fiber is not limited to pulp, and for example, synthetic fibers such as acrylic fiber, vinylon fiber, polypropylene fiber, and aramid fiber, and reinforcing fibers such as carbon fiber and glass fiber can be used in combination. Particularly when reinforcing fibers are used in combination, the mechanical strength is further improved, which is preferable.
上記のような補強繊維に対してなされる撥水処理は、適宜の手法で行うことができるが、特にシラン系撥水処理剤を用いて撥水処理を行うことが好ましい。シラン系撥水処理剤は、セメント複合材の成形時にセメントの硬化反応を阻害するなどの悪影響を及ぼすことがなく、セメント複合材の良好な成形性を維持することができ、またパルプとの吸着性にも優れているものである。このようなシラン系撥水処理剤としては、例えば東レダウコーニング社製の吸水防止剤「ＢＹ１６−６０６」を挙げることができる。また撥水処理剤を用いる場合には、このようなシラン系撥水処理剤に限られるものではなく、例えばシリコン系の撥水処理剤を用いることができる。 The water repellent treatment performed on the reinforcing fibers as described above can be performed by an appropriate method, but it is particularly preferable to perform the water repellent treatment using a silane-based water repellent treatment agent. Silane-based water repellent treatment agent can maintain the good formability of cement composites without causing adverse effects such as inhibiting the hardening reaction of cement during the molding of cement composites, and can also adsorb to pulp. It is also excellent in properties. Examples of such a silane-based water repellent treatment agent include a water absorption inhibitor “BY16-606” manufactured by Toray Dow Corning. Moreover, when using a water-repellent agent, it is not restricted to such a silane type water-repellent agent, For example, a silicon-type water-repellent agent can be used.
上記のような撥水処理剤による撥水処理は、例えば補強繊維を解繊する際に撥水処理剤を添加して、撥水処理剤により補強繊維の表面を被覆することができる。 In the water repellent treatment with the water repellent treatment agent as described above, for example, a water repellent treatment agent can be added when the reinforcing fiber is defibrated, and the surface of the reinforcing fiber can be covered with the water repellent treatment agent.
また、乳化剤（逆乳化剤）としては、組成物中の成分に応じて、Ｗ／Ｏエマルジョンを形成することができるように、適宜のものを用いることができるが、例えばソルビタンセスキオレート、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ート等の非イオン性界面活性剤、各種アニオン系界面活性剤、カチオン系界面活性剤等を用いることができる。このような乳化剤の含有量も適宜調整することができるが、好ましくは組成物中におけるセメント及び水（骨材を加える場合には更に骨材）の含有量の総量に対して１〜３体積％の範囲とするものである。 As the emulsifier (reverse emulsifier), an appropriate one can be used depending on the components in the composition so that a W / O emulsion can be formed. For example, sorbitan sesquioleate, glycerol monostearate Nonionic surfactants such as rate, sorbitan monooleate, diethylene glycol monostearate, sorbitan monostearate, and diglycerol monooleate, various anionic surfactants, and cationic surfactants can be used. The content of such an emulsifier can also be adjusted as appropriate, but is preferably 1 to 3% by volume based on the total content of cement and water (or aggregate in the case of adding aggregate) in the composition. It is set as the range.
また、組成物中には他に種々の添加剤を含有させることもでき、例えば砂、砂利、パーライト、シラスバルーン、ガラス粉等の骨材を含有させることができる。 In addition, various other additives can also be contained in the composition, and for example, aggregates such as sand, gravel, perlite, shirasu balloon, and glass powder can be contained.
尚、Ｗ／Ｏエマルジョンとは、油性物質と水とを撹拌混合することによって形成されるエマルジョンの内、油性物質の連続相の中に水が微小な水滴となって存在している状態を意味しており、本発明におけるＷ／Ｏエマルジョン組成物は、上記のＷ／Ｏエマルジョン中に更に無機質材が分散している状態のものである。 The W / O emulsion means a state in which water is present as fine water droplets in the continuous phase of the oily substance in the emulsion formed by stirring and mixing the oily substance and water. Therefore, the W / O emulsion composition in the present invention is in a state where an inorganic material is further dispersed in the W / O emulsion.
本発明のセメント複合材は、上記原材料を撹拌混合してＷ／Ｏエマルジョン組成物となし、次いでそれを注型法、押出成形法、射出成形法、プレス成形法等の通常用いられている手段で成形して、養生及び／又は重合硬化させた後、必要に応じて乾燥して製造することができる。 The cement composite of the present invention is a W / O emulsion composition obtained by stirring and mixing the above raw materials, and then a commonly used means such as a casting method, an extrusion molding method, an injection molding method, or a press molding method. After being cured and cured and / or polymerized and cured, it can be dried as necessary.
ここで、養生及び／又は重合硬化を行う際の条件は、適宜設定されるものであるが、例えば４０〜１００℃で２０〜４８時間、湿熱養生することができる。 Here, the conditions for curing and / or polymerization and curing are set as appropriate, but for example, the curing can be performed at 40 to 100 ° C. for 20 to 48 hours.
このようにして得られたセメント複合材は、Ｗ／Ｏエマルジョン組成物中の微小な水滴が除去された跡が、いわゆる独立気孔の形状で多数存在している。本発明における独立気孔という用語は、個々の気孔がそれぞれ別々に形成されて存在しているという意味であって、気孔の欠陥や穴による隙間が存在し、気孔同士や気孔と表面とがこの隙間によって繋がっていることを排除するものではない。 The cement composite obtained in this way has many traces of so-called independent pores in which minute water droplets in the W / O emulsion composition have been removed. The term “independent pore” in the present invention means that each individual pore is formed separately, and there is a pore defect or a gap due to the hole, and the pores or between the pore and the surface are this gap. It does not exclude being connected by.
また、得られたセメント複合材は、補強繊維が含有されて、優れた曲げ強度と耐凍害性とを有している。 Further, the obtained cement composite material contains reinforcing fibers and has excellent bending strength and frost damage resistance.
従って、このセメント複合材は、特に外装材として好適に用いることができる。 Therefore, this cement composite material can be suitably used particularly as an exterior material.
（実施例１、比較例１，２）
ポルトランドセメント、水、ビニルモノマーソリューション（ＶＭＳ；ビニルモノマー（スチレン）と乳化剤（ソルビタンモノオレート）とを、前者対後者の体積比率が５：２となるように混合した混合物）及びパルプ（ドライパルプ；常祐パルプ工業社製）を用い、下記表１に示す体積比率となるように組成物を調製した。
(Example 1, Comparative Examples 1 and 2)
Portland cement, water, vinyl monomer solution (VMS; mixture of vinyl monomer (styrene) and emulsifier (sorbitan monooleate) so that the volume ratio of the former to the latter is 5: 2) and pulp (dry pulp; The composition was prepared so that it might become the volume ratio shown in the following Table 1 using the product of the product of the Joyo pulp industry.
ここで、パルプはＮ材パルプを使用し、また実施例１においては、パルプには解繊処理時にシラン系の撥水処理剤（東レダウコーニングシリコーン株式会社製の吸水防止剤「ＢＹ１６−６０６」）を用いて、撥水処理を施した。 Here, N pulp is used for the pulp, and in Example 1, a silane-based water repellent treatment agent (a water absorption inhibitor “BY16-606” manufactured by Toray Dow Corning Silicone Co., Ltd.) is used for the pulp during the defibrating process. ) To give a water repellent treatment.
このようにして得られた組成物を押出成形し、６０℃、４８時間の条件で養生硬化させてセメント板を得た。 The composition thus obtained was extruded and cured by curing at 60 ° C. for 48 hours to obtain a cement board.
このようにして得られた各セメント板について、曲げ強度と、耐凍害性についての評価試験を行った。 Each cement board thus obtained was subjected to an evaluation test for bending strength and frost resistance.
曲げ強度はＪＩＳ Ａ １４０８の規定に準じ、５号試験片を用いて測定した。 The bending strength was measured using a No. 5 test piece according to JIS A 1408.
また、耐凍害性はＡＳＴＭ Ｃ６６６ Ｂ法に準拠して評価した。 The frost damage resistance was evaluated according to the ASTM C666 B method.
表２から明らかなように、実施例１は、パルプ繊維を撥水処理することで、成形性が良いものであり、耐凍害性、曲げ強度に優れたセメント板を得ることができた。 As can be seen from Table 2, in Example 1, the pulp fiber was water repellent treated, so that the moldability was good, and a cement board excellent in frost resistance and bending strength could be obtained.
比較例１は、撥水処理をしていないパルプ繊維を添加しているため、成形状態は、離水する傾向が見られ、硬化が不充分であり、十分な性能評価がでいなかった。 In Comparative Example 1, since pulp fibers not subjected to water repellent treatment were added, the molded state showed a tendency to separate water, the curing was insufficient, and sufficient performance evaluation could not be performed.
比較例２は、補強繊維を添加していないため、成形性には問題がないものの、曲げ強度は弱く、また、耐凍害性も非常に劣るものであった。 In Comparative Example 2, since no reinforcing fiber was added, although there was no problem in moldability, the bending strength was weak and the frost damage resistance was very poor.
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| JP3129970B2 (en) * | 1996-07-23 | 2001-01-31 | 大日精化工業株式会社 | Coating composition for surface water-repellent concrete, mold using the coating composition, and method for molding a concrete molding using the mold |
| JP3318491B2 (en) * | 1996-09-04 | 2002-08-26 | 信越化学工業株式会社 | Manufacturing method of lightweight inorganic plate |
| JPH11217561A (en) * | 1998-02-03 | 1999-08-10 | Shin Etsu Chem Co Ltd | Water repellent film-revivifying agent |
| JP4064593B2 (en) * | 1999-09-30 | 2008-03-19 | 三菱製紙株式会社 | Laminated sheet and filter medium with flame retardancy and low gas generation |
| JP2001270757A (en) * | 2000-03-27 | 2001-10-02 | Taiheiyo Cement Corp | Pillar-like body made from concrete |
| JP2002047040A (en) * | 2000-08-01 | 2002-02-12 | Okura Ind Co Ltd | Method of producing w/o emulsion containing cement |
| CZ20032693A3 (en) * | 2001-03-09 | 2004-07-14 | James Hardie Research Pty. Limited | Fiber reinforced cement composite materials employing chemically treated fibers exhibiting enhanced dispersing property |
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2003
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