JP2012017213A - Expansive solidifying material - Google Patents
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Abstract
Description
本発明は、セメントを用いる工事に汎用でき、セメントの固化による収縮で生じる不都合を防ぐことができる膨張性固化材に関する。 The present invention relates to an expandable solidifying material that can be used in general for construction using cement and can prevent inconvenience caused by shrinkage caused by cement solidification.
土木分野や建築分野の工事で汎用される基礎素材のセメントは、固化すると収縮する性質がある。この性質のため、セメントを用いる工事の種類によっては不都合を生じることがある。例えば、建造物を建てる際、地盤抵抗を得るために杭基礎などのコンクリート基礎が施工されるが、収縮により型枠の内壁との間や杭芯との間に隙間が生じることがある。隙間が生じることにより地盤との摩擦抵抗が下がるので、コンクリート基礎の支持力が低下するおそれがあり、また、過度な隙間が生じると、施工箇所へのセメントの二次・三次注入が必要となり、工事費の上昇や工期の長期化を招くことがある。 Cement, a basic material widely used in civil engineering and construction work, has the property of shrinking when solidified. This property may cause inconvenience depending on the type of construction using cement. For example, when building a building, a concrete foundation such as a pile foundation is constructed in order to obtain ground resistance, but a gap may be formed between the inner wall of the formwork or the pile core due to shrinkage. Since the frictional resistance with the ground is lowered due to the gap, the bearing capacity of the concrete foundation may be reduced, and when excessive gaps are generated, secondary and tertiary injection of cement to the construction site is required, The construction cost may increase and the construction period may be prolonged.
従来、生石灰が水と水和反応することにより膨張することを利用し、セメントの固化による収縮で生じる不都合に対応できる膨張性のセメントがある。補強対象地山の削孔にロックボルト材を固定するロックボルト工法において、生石灰の瞬時に起こる水和反応を遅延させる不飽和脂肪酸の油膜を外表面に形成した生石灰とセメントを水でスラリー状にした膨張性のセメントとして膨張性固化材を用いることの開示がある（特許文献１参照）。
また、生石灰に界面活性剤又は油脂を添加する反応遅延性生石灰の製造方法（特許文献２参照）や生石灰に高級脂肪酸を添加する反応遅延性生石灰の製造方法（特許文献３参照）の開示がある。
2. Description of the Related Art Conventionally, there is an expansive cement that utilizes the fact that quick lime expands by hydration reaction with water and can cope with inconvenience caused by shrinkage due to cement solidification. In the rock bolt method, in which rock bolt material is fixed to the drilled hole of the ground to be reinforced, quick lime and cement formed with an oil film of unsaturated fatty acid that delays the instantaneous hydration reaction of quick lime are slurried with water. There is a disclosure of using an expansive solidifying material as the expansive cement (see Patent Document 1).
Moreover, there is a disclosure of a reaction-retarded quicklime production method (see Patent Document 2) in which a surfactant or fat is added to quicklime and a reaction-retarded quicklime production method in which a higher fatty acid is added to quicklime (see Patent Document 3). .
しかし、特許文献１に開示の膨張性固化材は、セメントと不飽和脂肪酸の油膜で表面処理された生石灰の重量比が約２：１と生石灰の比率が高くセメントの比率は低いためセメントの固化後の強度が低く、例えば上記のコンクリート基礎のような工事では強度の点で使用することが難しく、セメントを用いる工事の種類によっては強度の点で使用が制約されることがあり、汎用性の点で問題がある。また、不飽和脂肪酸の油膜で表面処理された生石灰の割合が多いため、工事費が高くなることがある。さらに、オリーブ油やアマニ油などの不飽和脂肪酸油を用いるため、不飽和脂肪酸の油膜で表面処理された生石灰は粉状とはならないので、セメントと不飽和脂肪酸の油膜で表面処理された生石灰を均一に混合したものを予め準備しておくことが難しく、施工現場において、生石灰の外表面に不飽和脂肪酸の油膜を形成させる作業を行い、次いで当該生石灰にセメントを混合して水を加え調製する作業を行うことを前提とし、そのため施工現場における作業が繁雑で工期が長くなることがある。特許文献２及び特許文献３には、水和反応遅延剤として界面活性剤、油脂あるいは高級脂肪酸を用いる反応遅延性生石灰の開示があるが、当該反応遅延性生石灰とセメントからなる膨張性固化材についての開示はない。 However, the expandable solidified material disclosed in Patent Document 1 has a weight ratio of quick lime surface-treated with an oil film of cement and an unsaturated fatty acid of about 2: 1, and the ratio of quick lime is high and the ratio of cement is low. Later strength is low, for example, it is difficult to use in terms of strength in construction such as the above concrete foundation, and depending on the type of construction using cement, the use may be restricted in terms of strength, There is a problem in terms. Moreover, since there is much ratio of the quicklime surface-treated with the oil film of unsaturated fatty acid, construction cost may become high. Furthermore, since unsaturated fatty acid oils such as olive oil and linseed oil are used, the quick lime surface-treated with the oil film of unsaturated fatty acids does not become powdery, so the quick lime surface-treated with the oil film of cement and unsaturated fatty acid is evenly distributed. It is difficult to prepare a mixture of these in advance, and at the construction site, an operation to form an oil film of an unsaturated fatty acid on the outer surface of quicklime, and then a work to mix the quicklime with cement and add water Therefore, the work at the construction site is complicated and the construction period may be long. Patent Document 2 and Patent Document 3 disclose a reaction-retarded quicklime that uses a surfactant, oil or fat or higher fatty acid as a hydration reaction retarder. Regarding the expansive solidified material composed of the reaction-retarded quicklime and cement. There is no disclosure.
本発明は、上記の事情に鑑みなされたもので、セメントを用いる工事の種類により制約されない汎用性のある膨張性固化材を提供することを課題とする。また、工事費の低減化に資することのできる膨張性固化材を提供することを課題とする。さらに、取り扱い性に優れる膨張性固化材を提供することを課題とする。 This invention is made | formed in view of said situation, and makes it a subject to provide the expandable solidification material with the versatility which is not restrict | limited by the kind of construction using a cement. It is another object of the present invention to provide an expandable solidifying material that can contribute to a reduction in construction costs. Furthermore, it aims at providing the expansible solidification material which is excellent in a handleability.
上記の課題を解決するため、本発明者は検討を重ねた結果、本発明に想到した。すなわち、本発明は、セメントと１以上の高級脂肪酸からなる水和反応遅延剤で表面処理された生石灰とを含み、水和反応遅延剤の添加量は生石灰に対して４〜１０重量％であり、また、セメントと水和反応遅延剤で表面処理された生石灰の割合は重量比で８：２〜８．５：１．５であることを特徴とする膨張性固化材を要旨とする。 In order to solve the above-mentioned problems, the present inventor has come up with the present invention as a result of repeated studies. That is, the present invention includes cement and quicklime surface-treated with a hydration reaction retarder composed of one or more higher fatty acids, and the addition amount of the hydration reaction retarder is 4 to 10% by weight with respect to quicklime. The gist of the expandable solidified material is characterized in that the ratio of the quicklime surface-treated with the cement and the hydration reaction retarder is 8: 2 to 8.5: 1.5 by weight.
上記の発明において、水和反応遅延剤はオレイン酸、リノール酸、リノレン酸、パルミトオレイン酸、パルミチン酸及びステアリン酸の混合物でもよい。また、生石灰は、日本石灰協会の定める粗粒滴定法（２５ｇ法）に準拠した試験の開始１０分後の４Ｎ−ＨＣｌの滴定量が１４３ｍｌ以下の活性度を有するものでもよい。 In the above invention, the hydration reaction retarder may be a mixture of oleic acid, linoleic acid, linolenic acid, palmitooleic acid, palmitic acid and stearic acid. Moreover, quick lime may have the activity whose titer of 4N-HCl 10 minutes after the start of the test based on the coarse-grain titration method (25g method) which a Japan Lime Association establishes is 143 ml or less.
本発明の膨張性固化材は、セメントの固化による強度を十分に保持し、収縮で生じる不都合を防ぐことができるので、セメントを用いる工事の種類に制約されず汎用性がある。
本発明の膨張性固化材は、施工箇所へのセメントの二次・三次注入が不要で、また、水和反応遅延剤で表面処理された生石灰の割合も低いため、工事費の低減化に資することができる。本発明の膨張性固化材は、セメントと水和反応遅延剤で表面処理された生石灰を均一に混合したものを予め準備でき、施工現場では水を加えるだけでよいので、取り扱い性に優れ工期の短縮化に資することができる。
Since the expandable solidified material of the present invention can sufficiently retain the strength due to solidification of the cement and prevent inconvenience caused by shrinkage, it is versatile without being restricted by the type of construction using cement.
The expansible solidification material of the present invention does not require secondary or tertiary injection of cement into the construction site, and contributes to a reduction in construction costs because the ratio of quick lime surface-treated with a hydration reaction retarder is low. be able to. The expandable solidified material of the present invention can be prepared in advance by uniformly mixing cement and quicklime surface-treated with a hydration reaction retarder, and it is only necessary to add water at the construction site. It can contribute to shortening.
本発明の膨張性固化材は、セメントと水和反応遅延剤で表面処理された生石灰とから構成され、生石灰が水と水和反応をすることにより膨張する性質を利用し、セメントの固化による収縮で生じる不都合を防ぐことができる。生石灰は、水和反応が瞬時に起こるので、蒸気が噴出し危険であるばかりか直ちに膨張するためセメントの固化による収縮で生じる不都合を防ぐことができない。そのため、生石灰を水和反応遅延剤で表面処理することにより生石灰と水との接触を規制し、水和反応を遅延させるものである。 The expandable solidified material of the present invention is composed of cement and quicklime surface-treated with a hydration reaction retarder, and utilizes the property that quicklime expands by hydration reaction with water, and shrinkage due to cement solidification Can prevent inconvenience caused by. Since quick lime is instantly hydrated, the quick lime is not only dangerous for vapor but also expands immediately. Therefore, it cannot prevent inconvenience caused by shrinkage due to cement solidification. Therefore, surface treatment of quicklime with a hydration reaction retarder regulates the contact between quicklime and water and delays the hydration reaction.
本発明の膨張性固化材に係るセメントは、ポルトランドセメントが好ましく、ポルトランドセメントであれば特に限定されないが、普通ポルトランドセメントがより好ましい。 The cement according to the expandable solidifying material of the present invention is preferably Portland cement and is not particularly limited as long as it is Portland cement, but ordinary Portland cement is more preferable.
本発明の膨張性固化材に係る生石灰は、市販の生石灰を使用することができる。膨張性の点から、日本石灰協会の定める粗粒滴定法（２５ｇ法）に準拠した試験（石灰ハンドブック（ＣＤ−ＲＯＭ版）参照（刊行年月日：２００２年１１月１２日、発行者：日本石灰協会））の開始１０分後の４Ｎ−ＨＣｌの滴定量が１４３ｍｌ以下の活性度を有する生石灰が好ましい。 Commercial quicklime can be used for the quicklime which concerns on the expansible solidification material of this invention. From the viewpoint of expansibility, see the test based on the coarse-grain titration method (25 g method) established by the Japan Lime Association (Lime Handbook (CD-ROM version)) (Date of publication: November 12, 2002, Publisher: Japan The quicklime having an activity with a titer of 4N-HCl 10 minutes after the start of the lime association)) is not more than 143 ml.
生石灰を表面処理する水和反応遅延剤の高級脂肪酸は、具体的には、炭素数が１０以上の飽和高級脂肪酸、不飽和高級脂肪酸又はこれらの混合物である。飽和高級脂肪酸は、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキジン酸などを挙げることができ、不飽和高級脂肪酸はパルミトオレイン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸などを挙げることができる。 The higher fatty acid of the hydration reaction retarder for surface treatment of quicklime is specifically a saturated higher fatty acid having 10 or more carbon atoms, an unsaturated higher fatty acid, or a mixture thereof. Examples of saturated higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid. Unsaturated higher fatty acids include palmitooleic acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid. And eicosapentaenoic acid.
生石灰を表面処理する水和反応遅延剤の添加量は、生石灰に対し４〜１０重量％であり、６〜８重量％が好ましい。水和反応遅延剤の量が４重量％未満であると、生石灰の水和反応を遅延させる作用が十分でないからであり、１０重量％を超えると表面処理後の生石灰の状態が粒状又は塊状になり、セメントとの均一な混合を容易に行えないからである。 The addition amount of the hydration reaction retarder which surface-treats quicklime is 4 to 10 weight% with respect to quicklime, and 6 to 8 weight% is preferable. When the amount of the hydration reaction retarder is less than 4% by weight, the action of delaying the hydration reaction of quick lime is not sufficient. When the amount exceeds 10% by weight, the state of the quick lime after the surface treatment becomes granular or massive. This is because uniform mixing with cement cannot be easily performed.
セメントと水和反応遅延剤で表面処理された生石灰の割合は、重量比で８：２〜８．５：１．５である。セメントと水和反応遅延剤で表面処理された生石灰の割合が８：２より水和反応遅延剤で表面処理された生石灰の割合が多くなると固化したセメントの強度が低くなり、また、８．５：１．５より水和反応遅延剤で表面処理された生石灰の割合が少なくなるとセメントの固化による収縮を十分に防げないからである。 The ratio of the quicklime surface-treated with cement and the hydration reaction retarder is 8: 2 to 8.5: 1.5 by weight. When the ratio of the quicklime surface-treated with the hydration reaction retarder is larger than the ratio of the quicklime surface-treated with the cement and the hydration reaction retarder, the strength of the solidified cement decreases as the ratio of the quicklime surface-treated with the hydration reaction retarder increases. : If the ratio of quicklime surface-treated with a hydration reaction retarder is less than 1.5, shrinkage due to cement solidification cannot be sufficiently prevented.
次いで、本発明を実施例を挙げて説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated, this invention is not limited to a following example.
〔実施例１〕（生石灰の水和反応遅延剤による表面処理の検討）
５００ｍｌビーカーに生石灰（河合石灰工業株式会社製）の２００ｇを計り取った。この生石灰に対し不飽和高級脂肪酸（オレイン酸、リノール酸、リノレン酸、パルミトオレイン酸）と飽和高級脂肪酸（パルミチン酸、ステアリン酸）の混合物からなる水和反応遅延剤（ミヨシ油脂株式会社製、ＰＭ２００）の４ｇ（２重量％）、８ｇ（４重量％）、１２ｇ（６重量％）、１６ｇ（８重量％）、２０ｇ（１０重量％）、２４ｇ（１２重量％）、２８ｇ（１４重量％）、３２ｇ（１６重量％）、３６ｇ（１８重量％）、４０ｇ（２０重量％）をそれぞれ添加した。生石灰と水和反応遅延剤を混合したものを撹拌棒で５分間撹拌し（撹拌は１回転／秒）、水和反応遅延剤で表面処理された生石灰を得た。次いで、１００ｍｌジュアー瓶に２０℃４００ｍｌの蒸留水を入れ、撹拌羽根及び温度計をセットした。さらに、各濃度の水和反応遅延剤で表面処理された生石灰の１０２ｇ（２重量％）、１０４ｇ（４重量％）、１０６ｇ（６重量％）、１０８ｇ（８重量％）、１１０ｇ（１０重量％）、１１２ｇ（１２重量％）、１１４ｇ（１４重量％）、１１６ｇ（１６重量％）、１１８ｇ（１８重量％）、１２０ｇ（２０重量％）をそれぞれジュアー瓶内に投入し、０分後、１５分後の水和反応で上昇した温度を測定した。
[Example 1] (Investigation of surface treatment with quick hydration hydration retarder)
In a 500 ml beaker, 200 g of quick lime (manufactured by Kawai Lime Industry Co., Ltd.) was weighed. Hydration reaction retarder consisting of a mixture of unsaturated higher fatty acids (oleic acid, linoleic acid, linolenic acid, palmitooleic acid) and saturated higher fatty acids (palmitic acid, stearic acid) for this quicklime (made by Miyoshi Oil & Fats Co., Ltd., PM200) 4 g (2 wt%), 8 g (4 wt%), 12 g (6 wt%), 16 g (8 wt%), 20 g (10 wt%), 24 g (12 wt%), 28 g (14 wt%) ), 32 g (16 wt%), 36 g (18 wt%), and 40 g (20 wt%) were added. A mixture of quicklime and a hydration reaction retarder was stirred with a stir bar for 5 minutes (stirring was 1 revolution / second) to obtain quicklime surface-treated with a hydration reaction retarder. Subsequently, 400 ml of distilled water at 20 ° C. was placed in a 100 ml dewar, and a stirring blade and a thermometer were set. Furthermore, 102 g (2 wt%), 104 g (4 wt%), 106 g (6 wt%), 108 g (8 wt%), 110 g (10 wt%) of quicklime surface-treated with each concentration of hydration reaction retarder ), 112 g (12 wt%), 114 g (14 wt%), 116 g (16 wt%), 118 g (18 wt%), and 120 g (20 wt%), respectively, were put into a dewar, and after 0 minutes, 15 g The temperature increased by the hydration reaction after a minute was measured.
上記と同様の方法で上記の水和反応遅延剤に代えヒマシ油（伊藤製油株式会社製）で表面処理された生石灰を得、上記と同様の方法で０分後、１５分後の水和反応により上昇した温度を測定した。また、ブランクとして表面処理されない生石灰についても上記と同様の方法で０分後、１５分後の水和反応により上昇した温度を測定した。結果は、表１に示した。 In the same manner as described above, quick lime surface-treated with castor oil (manufactured by Ito Oil Co., Ltd.) was obtained instead of the hydration reaction retarder, and the hydration reaction after 0 minutes and 15 minutes by the same method as above. Was used to measure the elevated temperature. In addition, quick lime that was not surface-treated as a blank was also measured for the temperature increased by the hydration reaction after 0 minutes and 15 minutes in the same manner as described above. The results are shown in Table 1.
表１から、不飽和高級脂肪酸と飽和高級脂肪酸の混合物からなる水和反応遅延剤を４重量％以上添加すれば、水和反応を十分に遅延させることができた。一方、ヒマシ油で水和反応を十分に遅延させるには、１２重量％以上添加することが必要であり、コスト面で不利である。また、生石灰と水和反応遅延剤を均一に混合して膨張性固化材を施工現場でいちいち調製するのではなく、施工現場においては予め準備された膨張性固化材に水を加えるだけで施工ができるようにするには、水和反応遅延剤で表面処理された生石灰はセメントと均一に混合するのが容易な粉状であること好ましい。この観点から、水和反応遅延剤の添加量を４〜１０重量％にすれば、水和反応を十分に遅延させ、また、水和反応遅延剤で表面処理された生石灰を粉状とできることが判明した。 From Table 1, if 4 wt% or more of a hydration reaction retarder comprising a mixture of unsaturated higher fatty acid and saturated higher fatty acid was added, the hydration reaction could be sufficiently delayed. On the other hand, in order to sufficiently delay the hydration reaction with castor oil, it is necessary to add 12% by weight or more, which is disadvantageous in terms of cost. Also, instead of mixing the quick lime and the hydration reaction retarding agent uniformly and preparing the expandable solidified material at the construction site, construction can be done by simply adding water to the preliminarily prepared expandable solidified material at the construction site. In order to be able to do so, it is preferable that the quicklime surface-treated with a hydration retarder is in the form of a powder that can be easily mixed with cement. From this viewpoint, if the addition amount of the hydration reaction retarder is 4 to 10% by weight, the hydration reaction can be sufficiently delayed, and quick lime surface-treated with the hydration reaction retarder can be powdered. found.
〔実施例２〕（セメントと水和反応遅延剤で表面処理された生石灰の割合の検討）
セメントと水和反応遅延剤で表面処理された生石灰の割合を、固化した膨張性固化材の膨張率と強度を測定することにより検討した。
[Example 2] (Examination of proportion of quicklime surface-treated with cement and hydration retardant)
The proportion of quicklime surface-treated with cement and a hydration retarder was examined by measuring the expansion rate and strength of the solidified expandable solidified material.
生石灰（河合石灰工業株式会社製）を１０００ｇ計り取った。この生石灰に対し不飽和高級脂肪酸（オレイン酸、リノール酸、リノレン酸、パルミトオレイン酸）と飽和高級脂肪酸（パルミチン酸、ステアリン酸）の混合物からなる水和反応遅延剤（ミヨシ油脂株式会社製、ＰＭ２００）の４０ｇ（４重量％）、６０ｇ（６重量％）、８０ｇ（８重量％）、１００ｇ（１０重量％）をそれぞれ添加した。生石灰と水和反応遅延剤を混合したものをベンチニーダーを用いて５分間撹拌し水和反応遅延剤で表面処理された生石灰を得た。セメント（普通ポルトランドセメント、太平洋セメント株式会社製）と各濃度の水和反応遅延剤で表面処理された生石灰を重量比で、９：１、８．５：１．５、８：２、７：３、６：４となる量をそれぞれ混合し、ベンチニーダーを用いて５分間撹拌して膨張性固化材を得た。得られた各重量比の膨張性固化材に対し、水を４５重量％となるようにそれぞれ加えてスラリー状の水和物を得た。スラリー状の水和物を２００ｃｍ３計り取りパレットに流し入れ、膨張は２４時間以内に完了することを考慮し、大気中で２４時間養生した（拘束しない状態のまま）。養生後、固化した膨張性固化材を粉砕して水を張ったメスシリンダーに入れ、水の増加分を体積膨張率として読み取り、各重量比で混合した膨張性固化材の膨張率を算出した。結果は表２に示した。 1000 g of quick lime (manufactured by Kawai Lime Industry Co., Ltd.) was weighed. Hydration reaction retarder consisting of a mixture of unsaturated higher fatty acids (oleic acid, linoleic acid, linolenic acid, palmitooleic acid) and saturated higher fatty acids (palmitic acid, stearic acid) for this quicklime (made by Miyoshi Oil & Fats Co., Ltd., 40 g (4 wt%), 60 g (6 wt%), 80 g (8 wt%), and 100 g (10 wt%) of PM200) were added. A mixture of quicklime and a hydration reaction retarder was stirred for 5 minutes using a bench kneader to obtain quicklime surface-treated with a hydration reaction retarder. Cement (ordinary Portland cement, Taiheiyo Cement Co., Ltd.) and quick lime surface-treated with each concentration of hydration reaction retarder in a weight ratio of 9: 1, 8.5: 1.5, 8: 2, 7: The amounts of 3, 6: 4 were mixed and stirred for 5 minutes using a bench kneader to obtain an expandable solidified material. Water was added to the obtained expandable solidified material in each weight ratio so as to be 45% by weight to obtain slurry hydrates. The slurry-like hydrate was poured into a 200 cm 3 measuring pallet and cured for 24 hours in the atmosphere (while remaining unconstrained), considering that expansion would be completed within 24 hours. After curing, the solidified expandable solidified material was pulverized and placed in a graduated cylinder filled with water. The increase in water was read as the volume expansion rate, and the expansion rate of the expandable solidified material mixed at each weight ratio was calculated. The results are shown in Table 2.
生石灰（河合石灰工業株式会社製）を１０００ｇ計り取った。この生石灰に対し不飽和高級脂肪酸（オレイン酸、リノール酸、リノレン酸、パルミトオレイン酸）と飽和高級脂肪酸（パルミチン酸、ステアリン酸）の混合物からなる水和反応遅延剤（ミヨシ油脂株式会社製、ＰＭ２００）の１００ｇ（１０重量％）を添加した。生石灰と水和反応遅延剤を混合したものをベンチニーダーを用いて５分間撹拌し水和反応遅延剤で表面処理された生石灰を得た。セメント（普通ポルトランドセメント、太平洋セメント株式会社製）と水和反応遅延剤で表面処理された生石灰を重量比で、９：１、８．５：１．５、８：２、７：３、６：４となる量をそれぞれ混合し、ベンチニーダーを用いて５分間撹拌して膨張性固化材を得た。得られた各重量比の膨張性固化材に対し、水を４５重量％となるようにそれぞれ加えてスラリー状の水和物を得た。スラリー状の水和物をサミットモールド（５０ｍｍ（直径）×１００ｍｍ（高さ））に流し入れ、ラッピングして大気中で３日間養生した。養生後、固化した膨張性固化材の上面を膨張箇所が平らになるようにヘラで削り脱型した。「土の万能圧縮試験機」（株式会社マルイ製、ＭＩＳ−２２５−１−２６型）を用い、膨張性固化材の一軸圧縮強さを計測した（条件：ひずみ速度は１．００％／ｍｉｎ（１ｍｉｎ当たり試料の長さ１００ｍｍの１％ひずみが生じる速さ））。結果は表２に示した。 1000 g of quick lime (manufactured by Kawai Lime Industry Co., Ltd.) was weighed. Hydration reaction retarder consisting of a mixture of unsaturated higher fatty acids (oleic acid, linoleic acid, linolenic acid, palmitooleic acid) and saturated higher fatty acids (palmitic acid, stearic acid) for this quicklime (made by Miyoshi Oil & Fats Co., Ltd., 100 g (10 wt%) of PM200) was added. A mixture of quicklime and a hydration reaction retarder was stirred for 5 minutes using a bench kneader to obtain quicklime surface-treated with a hydration reaction retarder. 9: 1, 8.5: 1.5, 8: 2, 7: 3, 6 by weight ratio of cement (ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd.) and quicklime surface-treated with a hydration retarder : 4 amounts were mixed and stirred for 5 minutes using a bench kneader to obtain an expandable solidified material. Water was added to the obtained expandable solidified material in each weight ratio so as to be 45% by weight to obtain slurry hydrates. The slurry hydrate was poured into a summit mold (50 mm (diameter) × 100 mm (height)), lapped, and cured in the atmosphere for 3 days. After curing, the upper surface of the solidified expandable solidified material was scraped off with a spatula so that the expanded portion was flattened. The uniaxial compressive strength of the expandable solidified material was measured using a “earth universal compression tester” (manufactured by Marui Co., Ltd., MIS-225-1-26 type) (condition: strain rate is 1.00% / min. (Speed at which 1% strain of a sample length of 100 mm per minute is generated)). The results are shown in Table 2.
表２から、セメントと水和反応遅延剤で表面処理された生石灰の割合が９：１の場合、セメントの固化による収縮が見られ、膨張性固化材として不向きであった。セメントと水和反応遅延剤で表面処理された生石灰の割合が８．５：１．５〜６：４の場合、膨張率は１を越え、セメントの固化による収縮を防ぐことができた。一方、セメントと水和反応遅延剤で表面処理された生石灰の割合が７：３と６：４の場合、生石灰の割合が高くセメントの割合が低いため、セメントの固化による収縮を防ぐことができても強度が低く、セメントを用いる工事の種類によっては膨張性固化材として使用できないことがある。セメントと水和反応遅延剤で表面処理された生石灰の割合が８．５：１．５〜８：２の場合、セメントの固化による収縮を防ぐことができ、かつ十分な強度を保持できるので、セメントを用いる工事の種類に制約されず汎用性があり、膨張性固化材として有用である。 From Table 2, when the ratio of the quicklime surface-treated with the cement and the hydration reaction retarder was 9: 1, shrinkage due to solidification of the cement was observed, which was unsuitable as an expandable solidifying material. When the ratio of the quicklime surface-treated with cement and the hydration reaction retarder was 8.5: 1.5 to 6: 4, the expansion rate exceeded 1, and shrinkage due to cement solidification could be prevented. On the other hand, when the ratio of quicklime surface-treated with cement and a hydration reaction retarder is 7: 3 and 6: 4, the ratio of quicklime is high and the ratio of cement is low, so that shrinkage due to cement solidification can be prevented. However, the strength is low, and depending on the type of construction using cement, it may not be used as an expandable solidifying material. When the ratio of quicklime surface-treated with cement and a hydration reaction retarder is 8.5: 1.5-8: 2, shrinkage due to solidification of the cement can be prevented, and sufficient strength can be maintained. It is versatile and not limited by the type of construction using cement, and is useful as an expandable solidifying material.
〔実施例３〕（生石灰の活性度の検討）
日本石灰協会の定める粗粒滴定法（２５ｇ法）に準拠し生石灰の活性度を測定した。
粒径が５ｍｍ〜３０ｍｍの石灰石４ｋｇを電気炉で以下の温度でそれぞれ１８０分焼成し、生石灰Ａ〜生石灰Ｇの７種を得た。
生石灰Ａ：１０００℃、生石灰Ｂ：１０５０℃、生石灰Ｃ：１１００℃、生石灰Ｄ：１１５０℃、生石灰Ｅ：１２００℃、生石灰Ｆ：１２５０℃、生石灰Ｇ：１３００℃
[Example 3] (Examination of quick lime activity)
The activity of quick lime was measured according to the coarse grain titration method (25 g method) defined by the Japan Lime Association.
4 kg of limestone having a particle size of 5 mm to 30 mm was baked for 180 minutes at the following temperatures in an electric furnace, respectively, to obtain 7 types of quicklime A to quicklime G.
Quicklime A: 1000 ° C, Quicklime B: 1050 ° C, Quicklime C: 1100 ° C, Quicklime D: 1150 ° C, Quicklime E: 1200 ° C, Quicklime F: 1250 ° C, Quicklime G: 1300 ° C
生石灰Ａ〜生石灰Ｇをそれぞれ粗粉砕・縮分し、粒径が２ｍｍ〜１０ｍｍの範囲となるように調整した。各生石灰を２５ｇ計り取った。次いで、３０．０℃±０．４℃に維持された水道水１０００ｍｌを測定装置にセットされた２０００ｍｌ容量の樹脂容器に入れた。撹拌羽を５００ｒｐｍで回転させ、ブロモチモールブルー指示薬（ＢＴＢ指示薬）を測定装置に入れた。次いで、ストップウオッチを押すと同時に各生石灰を測定装置に投入し、４Ｎ−ＨＣｌの滴定を開始した。滴定開始から１０分経過した時の４Ｎ−ＨＣｌの滴定量を読み取った。結果は、表３に示した。 Quick lime A to quick lime G were coarsely pulverized and contracted, respectively, and the particle size was adjusted to be in the range of 2 mm to 10 mm. 25 g of each quicklime was measured. Subsequently, 1000 ml of tap water maintained at 30.0 ° C. ± 0.4 ° C. was put into a 2000 ml capacity resin container set in the measuring apparatus. The stirring blade was rotated at 500 rpm, and bromothymol blue indicator (BTB indicator) was put into the measuring apparatus. Next, simultaneously with pressing the stopwatch, each quicklime was put into the measuring apparatus, and titration of 4N-HCl was started. The titer of 4N-HCl when 10 minutes passed from the start of titration was read. The results are shown in Table 3.
〔実施例４〕（生石灰Ａ〜生石灰Ｇを含む膨張性固化材の膨張率の検討）
実施例３で得た生石灰Ａ〜生石灰Ｇをそれぞれ１０００ｇ計り取った。生石灰に対し不飽和高級脂肪酸（オレイン酸、リノール酸、リノレン酸、パルミトオレイン酸）と飽和高級脂肪酸（パルミチン酸、ステアリン酸）の混合物からなる水和反応遅延剤（ミヨシ油脂株式会社製、ＰＭ２００）の４０ｇ（４重量％）、６０ｇ（６重量％）、８０ｇ（８重量％）、１００ｇ（１０重量％）をそれぞれ添加した。生石灰と水和反応遅延剤を混合したものをベンチニーダーを用いて５分間撹拌し水和反応遅延剤で表面処理された生石灰を得た。セメント（普通ポルトランドセメント、太平洋セメント株式会社製）と各濃度の水和反応遅延剤で表面処理された生石灰を重量比で、８．５：１．５となる量をそれぞれ混合し、ベンチニーダーを用いて５分間撹拌して膨張性固化材を得た。得られた膨張性固化材に対し、水を４５重量％となるようにそれぞれ加えてスラリー状の水和物を得た。スラリー状の水和物を２００ｃｍ３計り取りパレットに流し入れ、膨張は２４時間以内に完了することを考慮し、大気中で２４時間養生した（拘束しない状態のまま）。養生後、固化した膨張性固化材を粉砕して水を張ったメスシリンダーに入れ、水の増加分を体積膨張率として読み取り、膨張性固化材の膨張率を算出した。また、セメントと６重量％の水和反応遅延剤で表面処理された生石灰を重量比で８：２となる量を混合して得られた膨張性固化材についても同様の方法で膨張率を検討した。結果は表４に示した。
[Example 4] (Examination of expansion coefficient of expandable solidified material containing quicklime A to quicklime G)
Each 1000 g of quicklime A to quicklime G obtained in Example 3 was weighed. Hydration lagging agent (PM200 manufactured by Miyoshi Oil & Fats Co., Ltd.) consisting of a mixture of unsaturated higher fatty acids (oleic acid, linoleic acid, linolenic acid, palmitooleic acid) and saturated higher fatty acids (palmitic acid, stearic acid) to quicklime. 40 g (4 wt%), 60 g (6 wt%), 80 g (8 wt%), and 100 g (10 wt%) were added. A mixture of quicklime and a hydration reaction retarder was stirred for 5 minutes using a bench kneader to obtain quicklime surface-treated with a hydration reaction retarder. Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd.) and quick lime surface-treated with each concentration of hydration reaction retarder were mixed in an amount of 8.5: 1.5 by weight, and the bench kneader was mixed. The mixture was stirred for 5 minutes to obtain an expandable solidified material. Water was added to the obtained expandable solidified material so as to be 45% by weight to obtain slurry hydrates. The slurry-like hydrate was poured into a 200 cm 3 measuring pallet and cured for 24 hours in the atmosphere (while remaining unconstrained), considering that expansion would be completed within 24 hours. After curing, the solidified expandable solidified material was pulverized and placed in a graduated cylinder filled with water, and the increase in water was read as the volume expansion rate to calculate the expansion rate of the expandable solidified material. In addition, the expansion rate of the expandable solidified material obtained by mixing cement and quick lime surface-treated with 6% by weight of a hydration retarder in an amount of 8: 2 by weight is examined in the same way. did. The results are shown in Table 4.
表４から、生石灰Ｄ〜生石灰Ｇは、膨張率が１以上あり、セメントの固化による収縮を防ぐことができた。実施例３の生石灰Ｄの結果から、日本石灰協会の定める粗粒滴定法（２５ｇ法）に準拠した試験の開始１０分後の４Ｎ−ＨＣｌの滴定量が１４３ｍｌ以下の活性度を有する生石灰が好ましいことが判明した。 From Table 4, quick lime D-quick lime G had an expansion coefficient of 1 or more, and could prevent shrinkage due to solidification of cement. From the result of quick lime D of Example 3, quick lime having an activity of titrating 4N-HCl 10 minutes after the start of the test based on the coarse grain titration method (25 g method) defined by the Japan Lime Association is 143 ml or less is preferable. It has been found.
本発明の膨張性固化材は、セメントの固化による強度を十分に保持して収縮で生じる不都合を防ぐことができ、セメントを用いる工事の種類により制約されることなく使用でき汎用性が高いので、セメントを工事に用いる土木分野や建築分野において有用である。 The expandable solidified material of the present invention can prevent the inconvenience caused by shrinkage by sufficiently holding the strength due to the solidification of the cement, and can be used without being restricted by the type of construction using the cement. It is useful in the field of civil engineering and construction using cement for construction.
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