JP7044996B2 - Hard additive for cement and its manufacturing method - Google Patents

Hard additive for cement and its manufacturing method Download PDF

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JP7044996B2
JP7044996B2 JP2018086997A JP2018086997A JP7044996B2 JP 7044996 B2 JP7044996 B2 JP 7044996B2 JP 2018086997 A JP2018086997 A JP 2018086997A JP 2018086997 A JP2018086997 A JP 2018086997A JP 7044996 B2 JP7044996 B2 JP 7044996B2
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和弘 狩野
智子 木虎
貴 上河内
恭子 伊藤
定人 菊池
有紀 平野
匡史 新杉
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Sumitomo Osaka Cement Co Ltd
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Description

本発明は、セメント用急硬性添加材及びその製造方法に関し、特に、任意のセメントに添加して、常温のみならず夏季のような高温であっても、セメントに良好な初期強度の発現を付与することができるとともに、所定の流動性を十分に確保して施工性に優れる、セメント用急硬性添加材及びその製造方法に関する。 The present invention relates to a hard-hardening additive for cement and a method for producing the same, and in particular, when added to any cement, imparts good initial strength to the cement not only at room temperature but also at high temperatures such as summer. The present invention relates to a hard-hardening additive for cement and a method for producing the same, which can sufficiently secure a predetermined fluidity and is excellent in workability.

近年、トンネルや地下空間の建設工事では、モルタルやコンクリート等のセメント混合物を、壁面や露出面に吹き付けてライニングし、壁面や露出面の崩落を防止する吹き付け施工工法が広く実施されている。
かかるコンクリート吹き付け工法においては、コンクリート等を調製し、それを取り扱う際に必要な最低限の可使時間(ハンドリングタイム)を確保するとともに、壁面や露出面に吹き付けた後に、コンクリート等を即時に硬化させる必要がある。
また、止水工事や緊急工事においても、モルタルやコンクリートの可使時間を確保するとともに、即時に硬化させる必要がある。
In recent years, in the construction work of tunnels and underground spaces, a spraying method of spraying a cement mixture such as mortar or concrete onto a wall surface or an exposed surface to lining the wall surface or the exposed surface to prevent the wall surface or the exposed surface from collapsing has been widely implemented.
In such a concrete spraying method, concrete, etc. is prepared, the minimum usable time (handling time) required for handling it is secured, and after spraying on the wall surface or exposed surface, the concrete, etc. is immediately hardened. I need to let you.
In addition, it is necessary to secure the usable time of mortar and concrete and to cure them immediately even in water stoppage work and emergency work.

従来、急硬性を有するセメントとして、ジェットセメント等の急硬性セメントを製造している。これらに使用されるクリンカとして、ジェットセメントクリンカ、C4A3を主成分とするアーウィン系クリンカ、CAを主成分とするアルミナセメントクリンカ等がある。
また、急硬性成分であるC12A7を主成分としたクリンカを溶融し、その後これを急冷することによって、非晶質C12A7を得る方法もある。
Conventionally, as a cement having a fast-hardening property, a hard-hardening cement such as a jet cement has been manufactured. Examples of the clinker used for these include a jet cement clinker, an Irwin clinker containing C4A3S as a main component, an alumina cement clinker containing CA as a main component, and the like.
There is also a method of obtaining amorphous C12A7 by melting a clinker containing C12A7, which is a rapidly hardening component, as a main component, and then quenching the clinker.

特に、従来のジェットセメントクリンカは、カルシウムシリケート相を主成分とし速硬性成分としてC11A7・CaF2を約20~30重量%含有するクリンカであり、C11A7CaF2やC4AF等の融液相を生成させてなるものである。従って、急硬性成分であるC12A7の含有量を、上記範囲以上とすると、融液相が多くなりすぎ、クリンカが溶融してしまい、例えば現状設備での製造が非常に困難となる。 In particular, the conventional jet cement clinker is a clinker containing calcium silicate phase as a main component and C11A7 / CaF2 as a fast-curing component in an amount of about 20 to 30% by weight, and is formed by producing a melt phase such as C11A7CaF2 or C4AF. Is. Therefore, if the content of C12A7, which is a rapidly hardening component, is set to the above range or more, the amount of the melt phase becomes too large and the clinker melts, which makes it very difficult to manufacture, for example, in the current equipment.

また、アーウィン系クリンカは、急硬性を有するアーウィン(C4A3)を70重量%以上含有することから急硬性セメント用クリンカとして利用されているが、その急硬性成分の特性により、特に、低温での急硬性に劣るという問題がある。
更に、CAを主成分とするアルミナセメントクリンカは、C12A7を主成分としたクリンカに比べると、急硬性が劣る。
Further, the Irwin-based clinker is used as a clinker for hard-hardening cement because it contains 70% by weight or more of Irwin (C4A3 S ) having a hard-hardening property. There is a problem that it is inferior in sharpness.
Further, the alumina cement clinker containing CA as a main component is inferior in rapid hardness to the clinker containing C12A7 as a main component.

急硬性クリンカとしては、特許第4616113号公報(特許文献1)に、還元雰囲気下での焼成前のC12A7またはC11A7・CaX2(Xはハロゲンを示す)の含有量が20~30質量%であって、該C12A7またはC11A7・CaX2(Xはハロゲンを示す)を、還元雰囲気下、1300~1380℃で焼成することにより、X線回折により測定した格子定数が11.93~11.96Åであることを特徴とする、急硬性クリンカが開示されている。 As for the fast-hardening clinker, Japanese Patent No. 4616113 (Patent Document 1) states that the content of C12A7 or C11A7 / CaX2 (X indicates halogen) before firing in a reducing atmosphere is 20 to 30% by mass. , C12A7 or C11A7 · CaX2 (X indicates halogen) was calcined at 1300 to 1380 ° C. in a reducing atmosphere, and the lattice constant measured by X-ray diffraction was 11.93 to 11.96 Å. A characteristic, hard-hardening clinker is disclosed.

更に、特許第3179702号公報(特許文献2)には、急硬性セメント、急結材、速硬性セメント、地盤改良材、マスキング材等に使用されるクリンカ組成物であって、鉱物相として、12CaO・7Al系のカルシウムアルミネートを主成分としたクリンカ原料に、Feを全体の0.1~9重量%、CaFを全体の0.1~9重量%含有共存させることによって低温融液相と高温融液相とを生成させ、且つTiOを全体の0.5~9重量%添加することによって該低温融液相と高温融液相との融液生成開始温度を低下させて焼成してなることを特徴とする急硬性クリンカ組成物が開示されている。 Further, Japanese Patent No. 3179702 (Patent Document 2) describes a clinker composition used for hard-hardening cement, quick-setting material, quick-hardening cement, ground improvement material, masking material, etc., and has 12CaO as a mineral phase.・ A clinker raw material containing 7Al 2 O 3 calcium aluminate as a main component contains 0.1 to 9% by weight of Fe 2 O 3 and 0.1 to 9% by weight of CaF 2 in coexistence. By forming a low-temperature melt phase and a high-temperature melt phase, and adding 0.5 to 9% by weight of TiO 2 to the whole, the start temperature of melt formation between the low-temperature melt phase and the high-temperature melt phase can be adjusted. Disclosed is a fast-hardening clinker composition characterized by being lowered and fired.

これら従来のセメントクリンカは、固相反応を促進させるため、融液相を積極的に生成させる必要があり、融液相が少ないと固相反応が進まずクリンカ鉱物生成がうまく進行しない。一方、融液相の過剰生成は、クリンカ製造上問題となるため、生成される融液相の量を一定の範囲に入るように調整する必要があった。
特に、上記特許文献2等のクリンカは、C12A7系鉱物含有量をジェットクリンカに比べて増加させたものであり、C12A7系鉱物相を固相反応により生成するものである。このときFeやTiを添加して適量の融液相を生成させてクリンカを得ている。
また、上記従来のクリンカのC12A7系鉱物は固溶体であり、FeやTiの含有によりC12A7系鉱物の固溶状態が変化し、このことは、C12A7系鉱物の水和活性に影響を及ぼす。
In these conventional cement clinker, it is necessary to positively generate a melt phase in order to promote the solid phase reaction, and if the amount of the melt phase is small, the solid phase reaction does not proceed and the clinker mineral production does not proceed well. On the other hand, excessive formation of the melt phase poses a problem in the production of clinker, so it is necessary to adjust the amount of the melt phase to be formed so as to be within a certain range.
In particular, the clinker of Patent Document 2 and the like has a C12A7-based mineral content increased as compared with the jet clinker, and produces a C12A7-based mineral phase by a solid-phase reaction. At this time, Fe and Ti are added to generate an appropriate amount of melt phase to obtain a clinker.
Further, the C12A7-based mineral of the conventional clinker is a solid solution, and the solid-dissolved state of the C12A7-based mineral changes depending on the content of Fe and Ti, which affects the hydration activity of the C12A7-based mineral.

しかし、常温のみならず夏季のような高温季において、所望する急硬性である、例えば3時間強度を十分に発現し、セメントの流動性を十分に確保することは難しかった。これはクリンカを製造するために必要な適量の融液相を生成させる条件と、急硬性成分の固溶状態、すなわち水和活性を最大とする条件とが必ずしも一致しないからであり、急硬性成分の水和活性を最大となるような設計が困難であることが関係する。
更に、これらのクリンカはセメントの製造に用いる材料であり、任意のセメントに後添加して、得られるセメントの水和活性を利用時に増大し、所望する任意の急硬性を得るのに用いられるものではない。
However, it has been difficult to sufficiently develop the desired rapid hardness, for example, strength for 3 hours, and to sufficiently secure the fluidity of cement not only at room temperature but also in high temperature season such as summer. This is because the conditions for producing an appropriate amount of melt phase required for producing clinker do not always match the solid solution state of the rapidly rigid component, that is, the conditions for maximizing the hydration activity, and the rapidly rigid component It is related to the difficulty of designing to maximize the hydration activity of.
Furthermore, these clinker are materials used in the production of cement and are used to post-add to any cement to increase the hydration activity of the resulting cement during utilization and to obtain any desired fast hardness. is not it.

特許第4616113号公報Japanese Patent No. 4616113 特許第3179702号公報Japanese Patent No. 3179702

本発明の目的は、常温のみならず夏季のような高温下で十分な強度を発現し、水和活性に優れて良好な急硬性能を示すとともに、所定の流動性を十分に確保して施工性に優れる、セメント用急硬性添加材及びその製造方法を提供することである。 An object of the present invention is to exhibit sufficient strength not only at room temperature but also at high temperature such as summer, exhibit excellent hydration activity and good rapid hardening performance, and secure sufficient fluidity for construction. It is an object of the present invention to provide a fast-hardening additive for cement and a method for producing the same, which have excellent properties.

請求項1記載のセメント用急硬性添加材は、C12A7系鉱物相を70質量%以上、C2Sを25質量%以下、C3Aを5質量%以下、CAを10質量%以下、C2ASを20質量%以下で含むことを特徴とする、セメント用急硬性添加材である。 The hard-hardening additive for cement according to claim 1 has a C12A7-based mineral phase of 70% by mass or more, C2S of 25% by mass or less, C3A of 5% by mass or less, CA of 10% by mass or less, and C2AS of 20% by mass or less. It is a hard-hardening additive for cement, which is characterized by containing in.

請求項記載のセメント用急硬性添加材は、更に、C4AFを0.5質量%以下で含むことを特徴とする、セメント用急硬性添加材である。 The hard-hardening additive for cement according to claim 1 is a hard-hardening additive for cement , further comprising C4AF in an amount of 0.5% by mass or less.

請求項記載のセメント用急硬性添加材は、CaO及びMgO並びに、残部の鉱物相の総質量が15質量%以下であることを特徴とする、セメント用急硬性添加材である。 The hard-hardening additive for cement according to claim 1 is a hard-hardening additive for cement, characterized in that the total mass of CaO and MgO and the remaining mineral phase is 15% by mass or less.

請求項記載のセメント用急硬性添加材は、請求項1記載のセメント用急硬性添加材において、更にFeを5質量%以下で含み、CIE色差式によって求めたL*値が、式L*≧-3.4×Fe+55の範囲であることを特徴とする、セメント用急硬性添加材である。 The hard-hardening additive for cement according to claim 2 is the hard-hardening additive for cement according to claim 1 , further containing Fe 2 O 3 in an amount of 5% by mass or less, and the L * value determined by the CIE color difference formula is , L * ≧ -3.4 × Fe 2 O 3 +55, which is a hard additive for cement.

請求項記載のセメント用急硬性添加材は、請求項1又は2記載のセメント用急硬性添加材において、CIE色差式によって求めたL*値が67~85であることを特徴とする、セメント用急硬性添加材である。 The hard-hardening additive for cement according to claim 3 is the hard-hardening additive for cement according to claim 1 or 2 , wherein the L * value determined by the CIE color difference formula is 67 to 85. It is a hard additive.

請求項記載のセメント用急硬性添加材の製造方法は、C12A7系鉱物相が70質量%以上、C2Sが25質量%以下、C3Aが5質量%以下、CAが10質量%以下、C2ASが20質量%以下、C4AFを0.5質量%以下、CaO及びMgO並びに、残部の鉱物相の総質量が15質量%以下となるように原料を配合して粉末化し、該粉末化原料を焼成して得られる焼成体のL*値が、式L*≧-3.4×Fe+55の範囲になるように、焼成時の酸素濃度を調整して焼成することを特徴とする、セメント用急硬性添加材の製造方法である。 The method for producing a hard-hardening additive for cement according to claim 4 has a C12A7-based mineral phase of 70% by mass or more, C2S of 25% by mass or less, C3A of 5% by mass or less, CA of 10% by mass or less, and C2AS of 20. Raw materials are blended and powdered so that the total mass of CaO and MgO and the remaining mineral phase is 15% by mass or less, C4AF is 0.5% by mass or less, and the powdered raw material is calcined. For cement, the oxygen concentration at the time of firing is adjusted so that the L * value of the obtained fired body is in the range of the formula L * ≧ -3.4 × Fe 2 O 3 +55. This is a method for producing a hard-hardening additive.

本発明のセメント用急硬性添加材は、任意のセメントと混合することにより、得られるモルタル等が、流動性を十分に確保して優れた施工性を得ることができるとともに、水和活性を向上させて所望される優れた3時間初期強度を示すことができる。
従って、急硬性用途において作業現場等で有効に適用することが可能となり、更に、本発明のセメント用急硬性添加材を所望する初期強度に応じて任意の量で簡便に調整添加することで、所望する急硬性を得る設計を行うことが容易となるとともに、常温のみならず、特に30℃以上の夏季等の高温時での施工性を良好とすることが可能となる。
また、本発明のセメント用急硬性添加材を用いたモルタル等の、例えばポンプ圧送性が良好となる流動性を有することが可能である。
By mixing the hard-hardening additive for cement of the present invention with any cement, the obtained mortar or the like can sufficiently secure fluidity to obtain excellent workability and improve hydration activity. It is possible to show the desired excellent initial intensity for 3 hours.
Therefore, it can be effectively applied at work sites and the like in hard-hardening applications, and further, the hard-hardening additive for cement of the present invention can be easily adjusted and added in an arbitrary amount according to a desired initial strength. In addition to facilitating the design to obtain the desired sharp hardness, it is possible to improve the workability not only at room temperature but also at high temperature such as summer of 30 ° C. or higher.
Further, it is possible to have a fluidity such as a mortar using the hard additive for cement of the present invention, which improves pumping property, for example.

本発明のセメント用急硬性添加材の製造方法は、上記本発明のセメント用急硬性添加材を有効に製造することができ、また特殊な装置や設備を必要とせず、既存の設備を利用して、上記本発明のセメント用急硬性添加材を経済的に有効に製造することができる。 The method for producing a hard-hardening additive for cement of the present invention can effectively manufacture the hard-hardening additive for cement of the present invention, does not require special equipment or equipment, and utilizes existing equipment. Therefore, the above-mentioned hard-hardening additive for cement of the present invention can be economically and effectively produced.

本発明を次の形態により説明するが、これらに限定されるものではない。
本発明のセメント用急硬性添加材は、C12A7系鉱物相を70質量%以上、C2Sを25質量%以下、C3Aを5質量%以下、CAを10質量%以下、C2ASを20質量%以下で含む、セメント用急硬性添加材である。
本発明のセメント用急硬性添加材は、C4AFは0.5質量%以下で含まれ、CaO(フリーライム)及びMgO(ペリクレース)並びに残部の鉱物相の総質量が15質量%以下である。
ここで、「残部の鉱物相」とは、セメント用急硬性添加材中のC12A7系鉱物相、C2S、C3A、CA、C2AS、CaO及びMgO以外の鉱物相を意味し、かかる「残部の鉱物相」は、初期水和反応には寄与しないものである。
The present invention will be described in the following form, but the present invention is not limited thereto.
The hard-hardening additive for cement of the present invention contains C12A7-based mineral phase in an amount of 70% by mass or more, C2S in an amount of 25% by mass or less, C3A in an amount of 5% by mass or less, CA in an amount of 10% by mass or less, and C2AS in an amount of 20% by mass or less. , A hard additive for cement.
The hard-hardening additive for cement of the present invention contains C 4AF in an amount of 0.5% by mass or less, and has a total mass of CaO (free lime) and MgO (periclase) and the remaining mineral phase of 15% by mass or less. ..
Here, the "remaining mineral phase" means a mineral phase other than C12A7-based mineral phase, C2S, C3A, CA, C2AS, CaO and MgO in the hard-hardening additive for cement, and the "remaining mineral phase" is used. "Does not contribute to the initial hydration reaction.

すなわち、本発明のセメント用急硬性添加材は、C12A7系鉱物相を主成分とする添加材であって、C2Sを25質量%以下、C3Aを5質量%以下、CAを10質量%以下、C2ASを20質量%以下で含み、好ましくは、C4AFを0.5質量%以下で含み、更に好ましくはCaO及びMgO並びにC2S、C3A、CA、C2AS以外の残部の鉱物相の総質量が15質量%以下であることにより、任意の市場で入手しうるセメントに添加して得られるモルタル等が、常温のみならず、高温域においても優れた流動性を確保して施工性に優れることができるものとなり、3時間初期強度も良好とすることが可能となる。 That is, the hard-hardening additive for cement of the present invention is an additive containing a C12A7-based mineral phase as a main component, and has C2S of 25% by mass or less, C3A of 5% by mass or less, CA of 10% by mass or less, and C2AS. Is contained in an amount of 20% by mass or less, preferably C4AF is contained in an amount of 0.5% by mass or less, and more preferably, the total mass of the remaining mineral phases other than CaO and MgO and C2S, C3A, CA and C2AS is 15% by mass or less. As a result, mortar and the like obtained by adding to cement that can be obtained in any market can secure excellent fluidity not only at room temperature but also in high temperature range and have excellent workability. It is possible to improve the initial strength for 3 hours.

本発明のセメント用急硬性添加材には、カルシウムアルミネート相であるC12A7系鉱物相が70質量%以上含まれ、好適には83質量%以上含まれる。
従って、C12A7系鉱物相を高含有量で含み且つ水和活性を向上させることができ、その結果、上記本発明の効果を十分に奏することができるものとなる。
上記C12A7系鉱物相の含有量が70質量%未満であると、十分な急硬性が得られず、初期強度が低下してしまい、本発明の上記効果が得られない。
ここで、C12A7系鉱物相は、C12A7やC11A7・CaX2(Xは、F、Cl、Br等のハロゲン)が該当し、またこれらの混合相であってもよい。
The hard-hardening additive for cement of the present invention contains 70% by mass or more, preferably 83% by mass or more, of a C12A7-based mineral phase which is a calcium aluminate phase.
Therefore, the C12A7-based mineral phase can be contained in a high content and the hydration activity can be improved, and as a result, the above-mentioned effect of the present invention can be sufficiently exhibited.
If the content of the C12A7-based mineral phase is less than 70% by mass, sufficient rapid hardness cannot be obtained, the initial strength is lowered, and the above-mentioned effect of the present invention cannot be obtained.
Here, the C12A7-based mineral phase corresponds to C12A7 or C11A7 / CaX2 (X is a halogen such as F, Cl, Br, etc.), and may be a mixed phase thereof.

また、本発明のセメント用急硬性添加材に含まれるC2Sは、25質量%以下、好ましくは20質量%以下であり、実質的に含まれないことが望ましく、C3Aは5質量%以下であり、実質的に含まれないことが望ましく、更にCAは10質量%以下、好ましくは5質量%以下であり、実質的に含まれないことが望ましく、C2ASは20質量%以下、好ましくは10質量%以下であり、実質的には含まれないことが望ましい。
上記各鉱物であるC2S、C3A、CA、C2ASが、それぞれ上記各含有範囲を超えて含まれると、セメント用急硬性添加材中に含まれるC12A7系鉱物の含有量が少なくなってしまい、本発明の上記効果を発揮することができなくなってしまう。
ここで、「実質的に含まれない」とは、これらの鉱物相が、原料中に含まれる不純物であるSiやCaリッチ又はAlリッチな原料を用いることにより生成される場合を妨げないという意味であり、積極的に生成して含有させるものではない。
Further, C2S contained in the hard-hardening additive for cement of the present invention is 25% by mass or less, preferably 20% by mass or less, and it is desirable that it is not substantially contained, and C3A is 5% by mass or less. It is desirable that it is not substantially contained, and further, CA is 10% by mass or less, preferably 5% by mass or less, and it is desirable that it is not substantially contained, and C2AS is 20% by mass or less, preferably 10% by mass or less. It is desirable that it is not substantially included.
If each of the above minerals, C2S, C3A, CA, and C2AS, is contained in excess of each of the above ranges, the content of the C12A7-based mineral contained in the hard-hardening additive for cement is reduced, and the present invention It becomes impossible to exert the above-mentioned effect of.
Here, "substantially free" means that these mineral phases are not prevented from being produced by using a raw material rich in Si, Ca or Al, which are impurities contained in the raw material. Therefore, it is not actively produced and contained.

また、かかるC12A7系鉱物相を主成分とし、C2S、C3A、CA、C2ASの含有量が一定以下の本発明のセメント用急硬性添加材は、更に、C4A3を実質的に含まないことが望ましい。
実質的に含まれないとは、上記と同様に、原料中に含まれる不純物であるSOにより生成される場合を妨げないという意味であり、積極的に生成して含有させるものではない。
なお、本明細書において、は、SOを意味し、SはSiOを意味するものである。
Further, it is desirable that the hard-hardening additive for cement of the present invention containing the C12A7-based mineral phase as a main component and having a C2S, C3A, CA, C2AS content of a certain level or less is substantially free of C4A3S. ..
The fact that it is not substantially contained means that it does not prevent the case where it is produced by SO 3 which is an impurity contained in the raw material, and does not mean that it is positively produced and contained.
In this specification, S means SO 3 and S means SiO 2 .

また、本発明のセメント用急硬性添加材中にはFeは実質的には含まれないことが望ましく、例えば、Feの含有量はFe酸化物換算で5質量%以下、好ましくは1.5質量%以下であるため、含有されるC4AFは0.5質量%以下である。実質的にはC4AFはほとんど生成されず含まれない。 Further, it is desirable that Fe 2 O 3 is not substantially contained in the hard-hardening additive for cement of the present invention. For example, the content of Fe is 5% by mass or less in terms of Fe 2 O 3 oxide. Since it is preferably 1.5% by mass or less, the contained C4AF is 0.5% by mass or less. Substantially, C4AF is hardly generated and is not included.

更に、本発明のセメント用急硬性添加材は、MgOと、CaOと、上記C2S、C3A、CA及びC2AS以外の鉱物相(残部の鉱物相)との合計含有量が15質量%以下、好ましくは12質量%以下であることが望ましい。
15質量%を超えると、セメント用急硬性添加材中に含まれるC12A7系鉱物の含有量が少なくなってしまい、本発明の上記効果を発揮することができなくなってしまう場合があり望ましくない。
Further, the hard-hardening additive for cement of the present invention has a total content of MgO, CaO, and mineral phases other than the above-mentioned C2S, C3A, CA and C2AS (remaining mineral phase) of 15% by mass or less, preferably 15% by mass or less. It is preferably 12% by mass or less.
If it exceeds 15% by mass, the content of the C12A7-based mineral contained in the hard-hardening additive for cement becomes small, and the above-mentioned effect of the present invention may not be exhibited, which is not desirable.

また更に、本発明のセメント用急硬性添加材は、下記式を満足する関係とすることにより、本発明の効果を更に有効に発現することができる。
L*≧―3.4×Fe+55
式中、L*は、本発明のセメント用急硬性添加材のCIE色差式によって求めた色差値(L*値)を示し、例えば、コニカミノルタジャパン(株)製の色彩色差計(CR-300)を用いて、CIE(国際照明委員会)で規定された明度(L*値)の値であり、Feは、含有されるFe量を酸化物換算したものである。
セメント用急硬性添加材を調製する際の焼成時の還元度が高すぎるとL*値が低下し、C12A7系の活性が低下して初期強度不足となってしまい、また、セメント用急硬性添加材中のFe含有量が、上記した含有範囲を超えて多く含むとL*値が低下するが、上記したFe含有範囲であれば、問題にはならない。
上記式は、Fe含有量によってL*値が低下する要素を取り除き、還元焼成によってL*値が低下する要素について範囲を示したものであり、L*値が上記式を満たすように焼成中の酸素濃度を調整するようにする。
Further, the hard-hardening additive for cement of the present invention can more effectively exhibit the effect of the present invention by satisfying the following formula.
L * ≧ −3.4 × Fe 2 O 3 +55
In the formula, L * indicates the color difference value (L * value) obtained by the CIE color difference formula of the rapid-hardening additive for cement of the present invention, and for example, a color difference meter (CR-300) manufactured by Konica Minolta Japan Co., Ltd. ) Is the value of the brightness (L * value) specified by the CIE (International Commission on Illumination), and Fe 2 O 3 is the oxide-converted amount of Fe contained.
If the degree of reduction during firing when preparing a hard additive for cement is too high, the L * value will decrease, the activity of the C12A7 system will decrease, and the initial strength will be insufficient. If the Fe 2 O 3 content in the material exceeds the above-mentioned content range, the L * value decreases, but if it is the above-mentioned Fe 2 O 3 content range, it does not matter.
The above formula shows the range for the elements whose L * value decreases due to the Fe 2 O 3 content and the elements whose L * value decreases due to reduction firing, so that the L * value satisfies the above formula. Try to adjust the oxygen concentration during firing.

更に、本発明のセメント用急硬性添加材は、CIE色差式によって求めたL*値が67~85である。
L*値が上記範囲外であると、含有されるC12A7系の活性が低下してしまい、初期強度発現性が劣ることとなり望ましくない。セメント用急硬性添加材中のFe含有量が、上記した含有範囲を超えて多く含むとL*値が低下するが、上記したFe含有範囲であれば、問題にはならず、L*値が67~85とすることができる。
Further, the hard-hardening additive for cement of the present invention has an L * value of 67 to 85 determined by the CIE color difference formula.
If the L * value is out of the above range, the activity of the contained C12A7 system is lowered, and the initial strength expression is deteriorated, which is not desirable. If the Fe 2 O 3 content in the hard-hardening additive for cement exceeds the above-mentioned content range, the L * value decreases, but if it is the above-mentioned Fe 2 O 3 content range, it does not matter. However, the L * value can be 67 to 85.

本発明のセメント用急硬性添加材は、生石灰、消石灰、石灰石等のカルシウム原料、水酸化アルミニウム、アルミナ、ボーキサイトやバンド頁岩等のアルミニウム原料、ドロマイト等のマグネシウム原料、必要に応じて配合する蛍石等のフッ素原料等を混合して粉砕し、または粉砕して混合し、この粉末混合物を成形して成形体を得て、これを電気炉等加熱炉等を用いて焼成し、冷却して、セメント用急硬性添加材を調製する。
なお、得られるセメント用急硬性添加材中に含まれるFeの原料となるもの(例えばベンガラ等)は積極的に配合しない。得られるセメント用急硬性添加材中に含まれるFeは、上記配合原料中に不純物として含有されることにより、結果として含まれる場合もあるもので、積極的に含有させるものではない。
The hard-hardening additive for cement of the present invention includes calcium raw materials such as fresh lime, slaked lime, and limestone, aluminum hydroxide, alumina, aluminum raw materials such as bauxite and band spores, magnesium raw materials such as dolomite, and fluorite to be blended as necessary. Fluorine raw materials such as, etc. are mixed and crushed, or crushed and mixed, and this powder mixture is molded to obtain a molded product, which is fired and cooled using a heating furnace such as an electric furnace. Prepare a hard additive for cement.
It should be noted that the material used as a raw material for Fe (for example, red iron oxide) contained in the obtained hardened additive for cement is not positively blended. Fe contained in the obtained hardened additive for cement may be contained as an impurity in the compounding raw material, and may be contained as a result, but is not positively contained.

具体的には、本発明のセメント用急硬性添加材は、配合原料を粉末化して混合し、混合粉末を成型して得られた成型体を、例えば1250~1400℃、好ましくは1300~1360℃の温度で十分に、例えば0.5~3時間焼成し、次いで40℃/分以下、好ましくは5~40℃/分の冷却速度により冷却することで製造することができる。なお、上記本発明における含量割合となるように、原料を配合する。
上記各鉱物の含有量を上記のように調整することで、常温及び高温時においての施工性に優れるとともに、3時間強度発現性に優れるものとなる。
Specifically, the hard-hardening additive for cement of the present invention is a molded product obtained by powdering and mixing the compounding raw materials and molding the mixed powder, for example, 1250 to 1400 ° C., preferably 1300 to 1360 ° C. It can be produced by firing sufficiently at the temperature of, for example, 0.5 to 3 hours, and then cooling at a cooling rate of 40 ° C./min or less, preferably 5 to 40 ° C./min. The raw materials are blended so as to have the content ratio in the present invention.
By adjusting the content of each of the above minerals as described above, the workability at room temperature and high temperature is excellent, and the strength development for 3 hours is excellent.

このように、原料混合粉末を焼成、必要に応じて成型した成型体を焼成して、例えば40℃/分以下、好ましくは5~40℃/分の冷却速度で冷却する。かかる焼成中の酸素濃度を測定するとともに、得られるセメント用急硬性添加材のL*値を測定し、L*≧―3.4×Fe+55を満足できるように、望ましくはL*値が上記67~85の範囲内となるように、焼成時に空気等を導入して、酸素濃度を調整して調整する。
即ち、流動性を良好として可使時間を確保するとともに急硬性を得るためには、上記焼成温度等で焼成し、上記冷却速度で冷却し、酸素濃度を調整することで、好適な本発明のセメント用急硬性添加材を得ることができることとなる。
In this way, the raw material mixed powder is fired, and if necessary, the molded body is fired and cooled at a cooling rate of, for example, 40 ° C./min or less, preferably 5 to 40 ° C./min. The oxygen concentration during such firing is measured, and the L * value of the obtained hardened cement additive is measured, so that L * ≧ −3.4 × Fe 2 O 3 +55 can be satisfied, preferably L *. Air or the like is introduced at the time of firing so that the value is within the range of 67 to 85, and the oxygen concentration is adjusted.
That is, in order to secure good fluidity and secure pot life and obtain rapid hardness, it is preferable to perform firing at the above-mentioned firing temperature or the like, cool at the above-mentioned cooling rate, and adjust the oxygen concentration. It is possible to obtain a quenching additive for cement.

本発明のセメント用急硬性添加材は、粉砕してセメント用急硬性添加材粉末とし、該粉末を任意のセメント、例えば、普通ポルトランドセメント等に硫酸塩等とともに配合して急硬性セメント組成物として利用することが可能である。
本発明のセメント用急硬性添加材は、ブレーン比表面積が4500cm/g以上に粉砕して用いることが好ましく、これは、4500cm/g未満では、良好な急硬性が得られない場合があるからである。
また、ブレーン比表面積は、大きくしすぎると流動性に悪影響を及ぼし、粉砕時間を要して生産性が低下しコスト高になるので、5000~7000cm/gが望ましい。
また、粉砕する際に、粉砕助剤(ジエチレングリコール、トリエタノールアミン等)を添加してもよい。
The hard-hardening additive for cement of the present invention is crushed into a hard-hardening additive powder for cement, and the powder is blended with arbitrary cement, for example, ordinary Portland cement or the like together with sulfate or the like to obtain a hard-hardening cement composition. It is possible to use it.
The hard-hardening additive for cement of the present invention is preferably used after being pulverized to a brain specific surface area of 4500 cm 2 / g or more, and if it is less than 4500 cm 2 / g, good hard-hardening may not be obtained. Because.
Further, if the specific surface area of the brain is too large, the fluidity is adversely affected, the crushing time is required, the productivity is lowered, and the cost is high. Therefore, 5000 to 7000 cm 2 / g is desirable.
Further, when pulverizing, a pulverizing aid (diethylene glycol, triethanolamine, etc.) may be added.

前記本発明のセメント用急硬性添加材が配合されるセメントとしては、市販されている任意のセメントを適用することができ、例えば、早強ポルトランドセメント、超早強ポルトランドセメント、普通ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント、耐硫酸塩ポルトランドセメント、フライアッシュセメント、高炉セメント、シリカセメント等から選ばれる少なくとも1種類を用いることができる。 Any commercially available cement can be applied as the cement to which the hard-hardening additive for cement of the present invention is blended, for example, early-strength Portland cement, ultra-early-strength Portland cement, ordinary Portland cement, and moderate. At least one selected from hot Portland cement, low heat Portland cement, sulfate resistant Portland cement, fly ash cement, blast furnace cement, silica cement and the like can be used.

また、硫酸塩としては、例えば、芒硝(硫酸ナトリウム)、硫酸カリウムなどのアルカリ金属硫酸塩、硫酸マグネシウム、石膏(硫酸カルシウム)などのアルカリ土類金属硫酸塩、硫酸アルミニウムなどが挙げられ、強度発現性の点から、石膏の使用が、あるいは石膏と芒硝の併用が好ましい。
石膏としては、無水石膏、半水石膏、二水石膏、またはこれらの混合物が例示できる。
また、その他必要に応じて配合が可能な材料として消石灰が挙げられる。
Examples of the sulfate include alkali metal sulfates such as Glauber's salt (sodium sulfate) and potassium sulfate, alkaline earth metal sulfates such as magnesium sulfate and gypsum (calcium sulfate), and aluminum sulfate. From the viewpoint of sex, the use of gypsum or the combined use of gypsum and Glauber's salt is preferable.
Examples of gypsum include anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, or a mixture thereof.
In addition, slaked lime can be mentioned as another material that can be blended as needed.

前記本発明のセメント用急硬性添加材、セメント、硫酸塩、水等の混合方法は、特に限定するものではなく、所定の割合に配合したのち、慣用の混合装置を用いて混合すれば良い。
また他に、凝結調整剤(リグニンスルホン酸系、オキシカルボン酸系、糖類等各種有機酸もしくは有機酸のアルカリ金属塩やアルカリ土類金属塩)や減水剤(アルキルアリルスルホン酸系、ナフタレンスルホン酸系、メラミンスルホン酸系、ポリカルボン酸系、AE減水剤、高性能減水剤、高性能AE減水剤も含む)等、液状または粉末状の混和剤や、細骨材(川砂、海砂、山砂、砕砂およびこれらの混合物)や、粗骨材(川砂利、海砂利、砕石およびこれらの混合物)等を配合することができる。
The method for mixing the hard-hardening additive for cement, cement, sulfate, water, etc. of the present invention is not particularly limited, and the mixture may be mixed in a predetermined ratio and then mixed using a conventional mixing device.
In addition, coagulation adjusters (lignin sulfonic acid type, oxycarboxylic acid type, various organic acids such as saccharides or alkali metal salts of organic acids and alkaline earth metal salts) and water reducing agents (alkylallyl sulfonic acid type, naphthalene sulfonic acid). Liquid or powder admixtures such as system, melamine sulfonic acid system, polycarboxylic acid system, AE water reducing agent, high performance water reducing agent, high performance AE water reducing agent, and fine aggregate (river sand, sea sand, mountain). Sand, crushed sand and a mixture thereof), coarse aggregate (river gravel, sea gravel, crushed stone and a mixture thereof) and the like can be blended.

このように本発明のセメント用急硬性添加材は、任意のセメントに添加することで、例えば、常温のみならず夏季のような高温での作業においても流動性を確保することができ施工性に優れるとともに、良好な3時間強度発現性を有し、所望する急硬性を現場で得ることができ、施工性を確保しつつ良好な初期強度発現性を得るための設計を極めて容易に操作することが可能となる。 As described above, by adding the hard-hardening additive for cement of the present invention to any cement, for example, fluidity can be ensured not only at room temperature but also at high temperature such as summer, and the workability can be improved. It is excellent, has good strength development for 3 hours, can obtain the desired sharp hardness in the field, and it is extremely easy to operate the design to obtain good initial strength development while ensuring workability. Is possible.

本発明を次の実施例、比較例及び試験例に基づき説明する。
(実施例1~19、比較例1~15)
1)セメント用急硬性添加材の調製
下記表1~3に示すように、石灰石、蛍石、水酸化アルミニウム、酸化鉄、酸化チタン及び珪砂の各原料を混合して粉末化して、加圧成形し、各成型体を電気炉にて、1300℃で30分間、表1~3に示す各酸素濃度で焼成し、次いで40℃/分の冷却速度で冷却して各セメント用急硬性添加材を得た
The present invention will be described with reference to the following examples, comparative examples and test examples.
(Examples 1 to 19, comparative examples 1 to 15)
1) Preparation of hard-hardening additive for cement As shown in Tables 1 to 3 below, raw materials of limestone, fluorite, aluminum hydroxide, iron oxide, titanium oxide and silica sand are mixed and powdered, and pressure-molded. Then, each molded product is calcined in an electric furnace at 1300 ° C. for 30 minutes at each oxygen concentration shown in Tables 1 to 3, and then cooled at a cooling rate of 40 ° C./min to obtain a fast-hardening additive for each cement. Obtained

2)セメント用急硬性添加材の鉱物の分析
得られた各セメント用急硬性添加材をX線回折/リートベルト法(装置:パナリティカル社製X’Pert MPD、解析ソフト:HighScorePlus)を用いて、C12A7系、C2S、C3A、CA、C2AS、C4AF、C4A3、CaO(フリーライム)及びMgO(ぺリクレース)の含有割合を測定した。その結果を、表1~3に示す。
なお、表中、前記鉱物以外の鉱物量を「その他」として表記した。
管電圧:45kV 管電流:40mA
2) Mineral analysis of hard-hardening additives for cement The obtained hard-hardening additives for cement were subjected to X-ray diffraction / Rietveld method (device: X'Pert MPD manufactured by PANalytical Co., Ltd., analysis software: HighScorePlus). , C12A7 series, C2S, C3A, CA, C2AS, C4AF, C4A3S , CaO (free lime) and MgO (periclase) were measured. The results are shown in Tables 1 to 3.
In the table, the amount of minerals other than the above minerals is indicated as "other".
Tube voltage: 45kV Tube current: 40mA

3)Fe成分の含有量の測定
得られた各セメント用急硬性添加材を、蛍光X線分析装置(パナリティカル社製;Axios)を用いて、JIS R 5204に準じて分析して、含有されるFe成分の含有割合を測定した。
その結果を、表1~3に示す。
但し、Fe成分は、セメント用急硬性添加材中に含まれるFeをFeとして換算して表示した。
3) Measurement of Fe component content The obtained hard-hardening additive for cement was analyzed and contained according to JIS R 5204 using a fluorescent X-ray analyzer (manufactured by PANalytical Co., Ltd .; Axios). The content ratio of the Fe component was measured.
The results are shown in Tables 1 to 3.
However, as the Fe component, Fe contained in the hard additive for cement was converted into Fe 2 O 3 and displayed.

4)色調の測定
得られた各セメント用急硬性添加材の色調を、コニカミノルタジャパン(株)製の色彩色差計(CR-300)を用いて、CIE(国際照明委員会)で規定された明度(L値)の値で測定した。その結果を、表1~3に示す。
4) Measurement of color tone The color tone of the obtained hard additive for cement was specified by the CIE (International Commission on Illumination) using a color difference meter (CR-300) manufactured by Konica Minolta Japan Co., Ltd. It was measured by the value of brightness (L value). The results are shown in Tables 1 to 3.

Figure 0007044996000001
Figure 0007044996000001

Figure 0007044996000002
Figure 0007044996000002

Figure 0007044996000003
Figure 0007044996000003

5)モルタルの調製
次いで、上記各セメント用急硬性添加材をブレーン比表面積が5200±200cm/g程度に粉砕して、各セメント用急硬性添加材粉末を得た。
早強セメント(HC:住友大阪セメント株式会社製)に、各セメント用急硬性添加材粉末、無水石膏(試薬、ブレーン比表面積6800cm/g)、NaSO(ぼう硝:試薬)及び消石灰(試薬)を、下記表4に示す配合割合にて配合してセメント組成物を調製した。
なお、前記各セメント組成物に、凝結調整剤(試薬;酒石酸、和光純薬工業(株)製)をセメント組成物に対して外割で表4に示す割合で配合するとともに水を、水/セメント組成物質量比が0.38となるように、下記表4のように配合して均一に混練し、各モルタルを得た。
5) Preparation of mortar Next, the above-mentioned hard-hardening additive for cement was pulverized to a brain specific surface area of about 5200 ± 200 cm 2 / g to obtain a hard-hardening additive powder for each cement.
Fast-hardening additive powder for each cement, anhydrous gypsum (reagent, brain specific surface area 6800 cm 2 / g), Na 2 SO 4 (reagent) and slaked lime in early-strength cement (HC: manufactured by Sumitomo Osaka Cement Co., Ltd.) (Reagent) was blended in the blending ratio shown in Table 4 below to prepare a cement composition.
A coagulation adjuster (reagent; tartrate acid, manufactured by Wako Pure Chemical Industries, Ltd.) was added to each of the cement compositions in the ratio shown in Table 4 by external division with respect to the cement composition, and water was added to the cement composition. As shown in Table 4 below, they were mixed and kneaded uniformly so that the cement composition substance amount ratio was 0.38, and each mortar was obtained.

Figure 0007044996000004
Figure 0007044996000004

(試験例)
1)強度測定及びフロー値測定
上記で得られた各モルタルについて、30℃での3時間強度(初期強度)及び30℃でのフロー値を、JIS R 5201に準じて測定した。
その結果も上記表1~3に示す。
(Test example)
1) Intensity measurement and flow value measurement For each mortar obtained above, the strength (initial intensity) at 30 ° C. for 3 hours and the flow value at 30 ° C. were measured according to JIS R 5201.
The results are also shown in Tables 1 to 3 above.

2)凝結時間
上記で得られた各モルタルについて、JIR R 5201(セメントの物理試験方法)に準じて各モルタルの終結時間を測定した。
但し、終結針は直径1インチ高さ2インチの円錐形針を用い、侵入深さが1.5mmになったときの時間を凝結(終結)時間とした。
2) Condensation time For each mortar obtained above, the condensation time of each mortar was measured according to JIR R5201 (physical test method for cement).
However, as the closing needle, a conical needle having a diameter of 1 inch and a height of 2 inches was used, and the time when the penetration depth became 1.5 mm was defined as the setting (closing) time.

上記試験で、フロー値が250mm以上、凝結時間が40分以上で且つ3時間強度が25N/mm以上の物性を有するものを◎とし、フロー値が200mm以上で、凝結時間が30分以上且つ3時間強度が20N/mm以上の物性を有するものを○として評価して、その評価結果も各表1~3に示す。 In the above test, those having a flow value of 250 mm or more, a setting time of 40 minutes or more and a strength of 25 N / mm 2 or more for 3 hours are marked with ⊚, and a flow value of 200 mm or more, a setting time of 30 minutes or more and a setting time of 30 minutes or more. Those having a physical property of 20 N / mm 2 or more for 3 hours are evaluated as ◯, and the evaluation results are also shown in Tables 1 to 3.

上記表1~3より、本発明の実施例のものは、常温のみならず夏季のような高温であっても、セメントに良好な初期強度の発現を付与することができるとともに、所定の流動性を十分に確保して施工性に優れることがわかる。 From Tables 1 to 3 above, the examples of the present invention can impart good initial strength to the cement not only at room temperature but also at high temperatures such as summer, and have a predetermined fluidity. It can be seen that it is excellent in workability by ensuring sufficient.

本発明のセメント用急硬性添加材を、任意のセメントに添加することで、常温のみならず夏季のような高温下においても、所望する急硬性を設計することが容易となり、トンネルや地下空間の建設工事や土木工事、止水工事、壁面等への吹き付け工事、緊急性を有する道路等の補修工事等、また土壌改良材として、所定のハンドリングタイムを確保しつつ、可使時間経過後には速やかに強度発現することが要求される作業箇所へ、有用に適用することができる。

By adding the hard-hardening additive for cement of the present invention to any cement, it becomes easy to design the desired hard-hardening not only at room temperature but also at high temperature such as summer, and it becomes easy to design the desired hardness in tunnels and underground spaces. Construction work, civil engineering work, water stoppage work, spraying work on walls, etc., repair work on urgent roads, etc., and as a soil improvement material, while ensuring a predetermined handling time, promptly after the pot life has elapsed It can be usefully applied to work places where strength is required to be exhibited.

Claims (4)

C12A7系鉱物相を70質量%以上、C2Sを25質量%以下、C3Aを5質量%以下、CAを10質量%以下、C2ASを20質量%以下、C4AFを0.5質量%以下で含み、CaO及びMgO並びに、残部の鉱物相の総質量が15質量%以下であることを特徴とする、セメント用急硬性添加材。 Contains 70% by mass or more of C12A7 mineral phase, 25% by mass or less of C2S, 5% by mass or less of C3A, 10% by mass or less of CA, 20% by mass or less of C2AS, 0.5% by mass or less of C4AF, and CaO. A rapid-hardening additive for cement, wherein the total mass of MgO and the remaining mineral phase is 15% by mass or less . 請求項1記載のセメント用急硬性添加材において、更にFeを5質量%以下で含み、CIE色差式によって求めたL*値が、式L*≧-3.4×Fe+55の範囲であることを特徴とする、セメント用急硬性添加材。 In the hard-hardening additive for cement according to claim 1 , Fe 2 O 3 is further contained in an amount of 5% by mass or less, and the L * value determined by the CIE color difference formula is the formula L * ≧-3.4 × Fe 2 O. A hard-hardening additive for cement, characterized by a range of 3 +55. 請求項1又は2記載のセメント用急硬性添加材において、CIE色差式によって求めたL*値が67~85であることを特徴とする、セメント用急硬性添加材。 The hard-hardening additive for cement according to claim 1 or 2 , wherein the L * value determined by the CIE color difference formula is 67 to 85. C12A7系鉱物相が70質量%以上、C2Sが25質量%以下、C3Aが5質量%以下、CAが10質量%以下、C2ASが20質量%以下、C4AFを0.5質量%以下、CaO及びMgO並びに、残部の鉱物相の総質量が15質量%以下となるように原料を配合して粉末化し、該粉末化原料を焼成して得られる焼成体のL*値が、式L*≧-3.4×Fe+55の範囲になるように、焼成時の酸素濃度を調整して焼成することを特徴とする、セメント用急硬性添加材の製造方法。 C12A7 mineral phase is 70% by mass or more, C2S is 25% by mass or less, C3A is 5% by mass or less, CA is 10% by mass or less, C2AS is 20% by mass or less , C4AF is 0.5% by mass or less, CaO and MgO. In addition, the L * value of the calcined product obtained by blending and pulverizing the raw materials so that the total mass of the remaining mineral phase is 15% by mass or less and calcining the pulverized raw materials is the formula L * ≧ -3. .. A method for producing a hard additive for cement, which comprises adjusting the oxygen concentration at the time of firing so as to be in the range of 4 × Fe 2 O 3 +55 and firing.
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