JP2002249352A - Alkali-free quick-setting admixture and cement composition - Google Patents
Alkali-free quick-setting admixture and cement compositionInfo
- Publication number
- JP2002249352A JP2002249352A JP2001039733A JP2001039733A JP2002249352A JP 2002249352 A JP2002249352 A JP 2002249352A JP 2001039733 A JP2001039733 A JP 2001039733A JP 2001039733 A JP2001039733 A JP 2001039733A JP 2002249352 A JP2002249352 A JP 2002249352A
- Authority
- JP
- Japan
- Prior art keywords
- alkali
- quick
- parts
- compound
- setting
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/001—Alkaline earth metal or Mg-compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0017—Refractory metal compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0022—Compounds of elements having a valency of 4
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1025—Alkali-free or very low alkali-content materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Lining And Supports For Tunnels (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、土木・建築業界に
おいて使用されるアルカリフリー急結剤及びセメント組
成物に関する。なお、本発明における(部)や(％)は特に
規定しない限り質量基準で示す。TECHNICAL FIELD The present invention relates to an alkali-free quick-setting agent and a cement composition used in the civil engineering and construction industries. In the present invention, (parts) and (%) are shown on a mass basis unless otherwise specified.
【０００２】[0002]
【従来の技術とその課題】トンネルの吹付け工法等に使
用されるセメント急結剤としては、カルシウムアルミネ
ートを主成分とし、その他に、炭酸ナトリウムやアルミ
ン酸ナトリウムを含有するものなど、これまでに数多く
提案された（特公昭56-27457号公報、特公平05-39899号
公報、特公平07-68057号公報、特開昭63-206341号公
報、及び特開昭63-236741号公報等）。これらのセメン
ト急結剤に含まれる炭酸ナトリウムやアルミン酸ナトリ
ウムはカルシウムアルミネートの反応を助長したり、そ
れ自身がゲル化してごく初期のこわばりを与えるもので
あり、セメント急結剤には欠くことのできない成分であ
ると考えられている。しかしながら、一方で、ナトリウ
ムなどのアルカリ金属はコンクリート中の骨材と反応
し、アルカリシリケートゲルを生成して膨潤し、膨張破
壊を招く、いわゆる、アルカリ骨材反応を引き起こすと
いう課題があった。2. Description of the Related Art As a cement quick-setting agent used in a tunnel spraying method, etc., those containing calcium aluminate as a main component, sodium carbonate or sodium aluminate, etc. (JP-B-56-27457, JP-B-05-39899, JP-B-07-68057, JP-A-63-206341, JP-A-63-236741, etc.) . Sodium carbonate and sodium aluminate contained in these cement quick-setting adjuvants promote the reaction of calcium aluminate and gel themselves to give very early stiffness. It is considered to be a component that cannot be used. However, on the other hand, there has been a problem that an alkali metal such as sodium reacts with the aggregate in the concrete, generates an alkali silicate gel, swells, and causes expansion failure, that is, causes a so-called alkali-aggregate reaction.
【０００３】そして、アルカリフリーであって、アルカ
リ金属を含有する急結剤と同等以上の急結性状を有する
急結剤の開発が待たれているのが現状である。At present, development of a quick-setting agent that is alkali-free and has a quick-setting property equal to or higher than that of a quick-setting agent containing an alkali metal is awaited.
【０００４】本発明者は、このような状況を鑑み、前記
課題を解消すべく種々検討した結果、特定の急結剤がア
ルカリフリーであって、従来のアルカリ含有のセメント
急結剤と同等以上の急結性状を有することを知見し、本
発明を完成するに至った。In view of such circumstances, the present inventors have conducted various studies to solve the above-mentioned problems. As a result, the specific quick-setting agent is alkali-free and is equal to or more than the conventional alkali-containing cement quick-setting agent. The present inventors have found that the present invention has a quick-setting property, and completed the present invention.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明は、４Ａ族
元素の溶解性化合物とカルシウムアルミネート類とを含
有してなるアルカリフリー急結剤であり、４Ａ族元素が
チタニウム又はジルコニウムである該アルカリフリー急
結剤であり、４Ａ族元素が４価である該アルカリフリー
急結剤であり、さらに、カルシウム化合物及び／又はア
ルミニウム化合物を含有してなる該アルカリフリー急結
剤であり、セメントと該アルカリフリー急結剤とを含有
してなるセメント組成物である。That is, the present invention is an alkali-free quick-setting agent containing a soluble compound of a Group 4A element and calcium aluminates, and the Group 4A element is titanium or zirconium. The alkali-free quick-setting agent, wherein the group 4A element is tetravalent, and the alkali-free quick-setting agent further comprises a calcium compound and / or an aluminum compound; And a cement composition containing the alkali-free quick-setting agent.
【０００６】[0006]
【発明の実施の形態】以下、本発明をさらに詳しく説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
【０００７】本発明で使用する４Ａ族元素の溶解性化合
物とは、チタニウム、ジルコニウム、及びハフニウムな
どの溶解性化合物が挙げられ、固形物でも液状でも使用
可能である。４Ａ族元素の溶解性化合物（以下、４Ａ族
化合物という）の具体例としては、硫酸チタニウム、塩
化チタニウム、臭化チタニウム、ヨウ化チタニウム、及
びホウ酸チタニウムなどのチタニウム化合物、硫酸ジル
コニウム、塩化ジルコニウム、硝酸ジルコニウム、フッ
化ジルコニウム、臭化ジルコニウム、ヨウ化ジルコニウ
ム、及び二塩化酸化ジルコニウムなどのジルコニウム化
合物、並びに、二塩化酸化ハフニウムやフッ化ハフニウ
ムなどのハフニウム化合物等が挙げられ、これらのうち
の一種又は二種以上が使用可能である。一方、４Ａ族元
素の化合物であっても、二酸化チタニウムや二酸化ジル
コニウムなどの酸化物、窒化チタニウムや窒化ジルコニ
ウムなどの窒化物、あるいは、炭化チタニウムや炭化ジ
ルコニウムなどの炭化物に代表される不溶性化合物で
は、凝結促進効果は得られない。４Ａ族元素は、主に、
３価と４価の化合物を形成するが、凝結促進効果が優れ
ることから、４価の化合物が好ましい。その具体例とし
ては、４価の硫酸チタニウム、４価の塩化チタニウム、
４価の硫酸ジルコニウム、及び４価の塩化ジルコニウム
などが挙げられ、これらのうちの一種又は二種以上を使
用することが好ましく、入手のしやすさから、また、塩
素を含まず、鉄筋コンクリートへの利用も可能であるな
どの利点があることから、４価の硫酸チタニウムを使用
することがより好ましい。４価の硫酸チタニウムには、
一般に、TiOSO4・nH2Oで表され、硫酸チタニルとも呼ば
れる白色結晶の化合物や、Ti(SO4)2・nH2Oで表され、単
に硫酸チタンとも呼ばれる化合物等がある。工業製品と
しての一般的な硫酸チタニウムは結晶質であって、その
組成は、例えば、TiO2分が25〜35％、全H2SO4分が47〜5
3％、付着硫酸が約10％、付着水分が約10％である。The soluble compound of the Group 4A element used in the present invention includes soluble compounds such as titanium, zirconium, and hafnium, and can be used as a solid or liquid. Specific examples of the soluble compound of the Group 4A element (hereinafter, referred to as Group 4A compound) include titanium compounds such as titanium sulfate, titanium chloride, titanium bromide, titanium iodide, and titanium borate; zirconium sulfate, zirconium chloride; Zirconium nitrate, zirconium fluoride, zirconium bromide, zirconium iodide, and zirconium compounds such as zirconium dichloride, and hafnium compounds such as hafnium dichloride and hafnium fluoride, and one or more of these. Two or more can be used. On the other hand, even in the case of compounds of the 4A group element, insoluble compounds represented by oxides such as titanium dioxide and zirconium dioxide, nitrides such as titanium nitride and zirconium nitride, and carbides such as titanium carbide and zirconium carbide, No coagulation promoting effect is obtained. Group 4A elements are mainly
Although trivalent and tetravalent compounds are formed, tetravalent compounds are preferred because of excellent coagulation promoting effect. Specific examples thereof include tetravalent titanium sulfate, tetravalent titanium chloride,
Examples thereof include tetravalent zirconium sulfate and tetravalent zirconium chloride, and it is preferable to use one or more of these. From the viewpoint of availability, the chlorine-free and reinforced concrete It is more preferable to use tetravalent titanium sulfate because it has advantages such as availability. For tetravalent titanium sulfate,
In general, represented by TiOSO 4 · nH 2 O, and compounds of white crystals, also referred to as titanyl sulfate, Ti is represented by (SO 4) 2 · nH 2 O, simply as compounds, also known as titanium sulfate. Typical titanium sulfate as an industrial product be crystalline, the composition may, for example, TiO 2 minutes 25 to 35% and the total H 2 SO 4 minutes 47-5
3%, attached sulfuric acid about 10%, attached moisture about 10%.
【０００８】本発明で使用するカルシウムアルミネート
類（以下、ＣＡ類という）とは、CaOとAl2O3を主成分と
し、水和活性を有する化合物の総称であり、CaO及び／
又はAl2O3の一部が、アルカリ金属酸化物、アルカリ土
類金属酸化物、酸化ケイ素、酸化チタン、酸化鉄、アル
カリ金属ハロゲン化物、アルカリ土類金属ハロゲン化
物、アルカリ金属硫酸塩、及びアルカリ土類金属硫酸塩
等と置換した化合物、あるいは、CaOとAl2O3を主成分と
するものにこれらが少量固溶した物質であり、ＣＡ類は
結晶質、非晶質のいずれであってもよい。結晶質の具体
例としては、例えば、CaOをC、Al2O3をA、R2O（Na2O、K
2O、Li2O）をRとすると、C3Aやこれにアルカリ金属が固
溶したC14RA5、CAやC12A7やC11A7・CaF2、C4A・Fe2O3、
及びC3A3・CaSO4などが挙げられるが、急結性が良好であ
ることから、非晶質のカルシウムアルミネート類が好ま
しい。なお、本発明はアルカリフリー急結剤に係るもの
であるが、工業原料からは微量のアルカリ金属が混入
し、前記のアルカリ金属を含むＣＡ類が一部生成する可
能性があるが、本発明では、これらのわずかなアルカリ
金属の存在によって何ら制限を受けるものではない。即
ち、ポルトランドセメントと同程度のアルカリ金属酸化
物の含有量、具体的には、アルカリ金属酸化物の合計量
がアルカリフリー急結剤100部中、２部以下の範囲であ
れば問題とはならない。また、アルカリ金属であって
も、リチウムは、アルカリ骨材反応による膨潤を起こさ
ないばかりか、むしろ、ナトリウムやカリウムにより引
き起こされるアルカリ骨材反応による膨潤を抑制する役
割を果たすため、その含有量に何ら制限を受けるもので
はない。ＣＡ類は、CaO原料とAl2O3原料、さらに必要に
応じて他の原料を配合し、熱処理して得られる。熱処理
方法は、特に限定されるものではないが、例えば、ロー
タリーキルンや電気炉等を使用する方法が挙げられ、熱
処理温度は特に限定されるものではないが、通常、1,00
0〜1,700℃程度で行われ、1,100〜1,600℃程度で行われ
ることが多い。ＣＡ類の粒度は、特に限定されるもので
はないが、ブレーン比表面積値（以下、ブレーン値とい
う）で3,000〜9,000cm2/gが好ましく、5,000〜8,000cm2
/gがより好ましい。3,000cm2/g未満では充分な急結性が
得られない場合があり、9,000cm2/gを超えるように粉砕
することはコスト高となり好ましくない。[0008] Calcium aluminates (hereinafter referred to as CAs) used in the present invention are a general term for compounds having CaO and Al 2 O 3 as main components and having hydration activity, and CaO and / or
Or part of Al 2 O 3 is an alkali metal oxide, an alkaline earth metal oxide, silicon oxide, titanium oxide, iron oxide, an alkali metal halide, an alkaline earth metal halide, an alkali metal sulfate, and an alkali. Compounds substituted with earth metal sulfates, etc., or substances containing CaO and Al 2 O 3 as main components, in which a small amount of these are dissolved, and CAs are either crystalline or amorphous. Is also good. Specific examples of crystalline materials include, for example, C for CaO, A for Al 2 O 3 , and R 2 O (Na 2 O, K
When R is 2 O, Li 2 O), C 3 A or C 14 RA 5 in which alkali metal is dissolved therein, CA, C 12 A 7 , C 11 A 7 · CaF 2 , C 4 A · Fe 2 O 3 ,
And C 3 A 3 .CaSO 4 , but amorphous calcium aluminates are preferred because of their quick setting properties. Although the present invention relates to an alkali-free quick-setting admixture, trace amounts of alkali metals may be mixed from industrial raw materials, and the above-mentioned CAs containing alkali metals may be partially generated. Then, there is no limitation by the presence of these slight alkali metals. That is, there is no problem if the content of the alkali metal oxide is about the same as that of Portland cement, specifically, if the total amount of the alkali metal oxides is within 2 parts in 100 parts of the alkali-free quick-setting agent. . Further, even in the case of an alkali metal, lithium not only does not cause swelling due to an alkali-aggregate reaction, but also has a role of suppressing swelling due to an alkali-aggregate reaction caused by sodium or potassium. There are no restrictions. CAs can be obtained by blending a CaO raw material, an Al 2 O 3 raw material, and, if necessary, other raw materials and subjecting them to a heat treatment. The heat treatment method is not particularly limited, and includes, for example, a method using a rotary kiln or an electric furnace, and the heat treatment temperature is not particularly limited.
It is performed at about 0 to 1,700 ° C, and is often performed at about 1,100 to 1,600 ° C. The particle size of the CAs is not particularly limited, but is preferably from 3,000 to 9,000 cm 2 / g in terms of a Blaine specific surface area (hereinafter referred to as a Blaine value), and is preferably from 5,000 to 8,000 cm 2.
/ g is more preferred. If it is less than 3,000 cm 2 / g, sufficient quick-setting properties may not be obtained, and pulverization so as to exceed 9,000 cm 2 / g is not preferable because of high cost.
【０００９】本発明で使用するカルシウム化合物及び／
又はアルミニウム化合物（以下、Ca化合物類という）の
具体例としては、例えば、酸化カルシウム、水酸化カル
シウム、塩化カルシウム、炭酸カルシウム、硫酸カルシ
ウム、亜硫酸カルシウム、硝酸カルシウム、及び亜硝酸
カルシウムなどのカルシウム化合物、酸化アルミニウ
ム、水酸化アルミニウム、塩化アルミニウム、硫酸アル
ミニウム、塩基性硫酸アルミニウム、硝酸アルミニウ
ム、亜硝酸アルミニウム、及びオキシ水酸化アルミニウ
ムなどのアルミニウム化合物が挙げられる。本発明で
は、これらのうちの一種又は二種以上を使用することが
できるが、塩素を含まず、鉄筋コンクリート構造物への
使用も可能である面から、酸化カルシウム、水酸化カル
シウム、硫酸カルシウム、亜硫酸カルシウム、硝酸カル
シウム、亜硝酸カルシウム、酸化アルミニウム、水酸化
アルミニウム、硫酸アルミニウム、塩基性硫酸アルミニ
ウム、硝酸アルミニウム、亜硝酸アルミニウム、及びオ
キシ水酸化アルミニウムが好ましく、急結性能の面か
ら、水酸化アルミニウム、硫酸アルミニウム、及び塩基
性硫酸アルミニウムがより好ましい。The calcium compound used in the present invention and / or
Or specific examples of aluminum compounds (hereinafter, referred to as Ca compounds) include, for example, calcium compounds such as calcium oxide, calcium hydroxide, calcium chloride, calcium carbonate, calcium sulfate, calcium sulfite, calcium nitrate, and calcium nitrite; Examples include aluminum compounds such as aluminum oxide, aluminum hydroxide, aluminum chloride, aluminum sulfate, basic aluminum sulfate, aluminum nitrate, aluminum nitrite, and aluminum oxyhydroxide. In the present invention, one or more of these can be used, but from the viewpoint of not containing chlorine and being usable for reinforced concrete structures, calcium oxide, calcium hydroxide, calcium sulfate, and sulfurous acid are used. Calcium, calcium nitrate, calcium nitrite, aluminum oxide, aluminum hydroxide, aluminum sulfate, basic aluminum sulfate, aluminum nitrate, aluminum nitrite, and aluminum oxyhydroxide are preferable.From the viewpoint of quick-setting performance, aluminum hydroxide, Aluminum sulfate and basic aluminum sulfate are more preferred.
【００１０】本発明のアルカリフリー急結剤（以下、本
急結剤という）は、４Ａ族化合物とＣＡ類、さらに、必
要に応じCa化合物類を含有するものである。本急結剤の
各成分の配合割合は特に限定されるものではないが、４
Ａ族化合物は、通常、本急結剤100部中、５〜30部が好
ましく、10〜20部がより好ましい。５部未満では初期の
凝結が充分でなく、リバウンドが大きくなる場合があ
り、30部を超えて使用すると強度発現性が悪くなる場合
がある。また、ＣＡ類は、通常、本急結剤100部中、40
〜80部が好ましく、50〜70部がより好ましい。40部未満
では凝結の終結が遅くなる場合があり、80部を超えると
強度発現性が悪くなる場合がある。さらに、Ca化合物類
は、通常、０〜40部が好ましく、５〜30部がより好まし
い。40部を超えて使用すると凝結の始発、終結共に遅く
なる場合がある。The alkali-free quick-setting agent of the present invention (hereinafter, referred to as "the quick-setting agent") contains a 4A group compound and CAs, and if necessary, Ca compounds. The mixing ratio of each component of the quick-setting binder is not particularly limited,
Usually, the group A compound is preferably 5 to 30 parts, more preferably 10 to 20 parts, in 100 parts of the quick-setting binder. If the amount is less than 5 parts, the initial setting is not sufficient, and the rebound may be large. If the amount exceeds 30 parts, the strength development may be deteriorated. In addition, CAs are usually contained in 40 parts of the instant binder in 40 parts.
-80 parts is preferable and 50-70 parts is more preferable. If the amount is less than 40 parts, the termination of the setting may be delayed, and if it exceeds 80 parts, the strength expression may be poor. Further, the Ca compounds are usually preferably 0 to 40 parts, more preferably 5 to 30 parts. If used in excess of 40 parts, both the onset and the end of setting may be delayed.
【００１１】本急結剤の使用量は、セメント100部に対
して、３〜15部が好ましく、５〜10部がより好ましい。
３部未満では充分な凝結促進効果が得られない場合があ
り、15部を超えて使用してもさらなる効果の増進が期待
できない。The amount of the quick-setting binder used is preferably 3 to 15 parts, more preferably 5 to 10 parts, per 100 parts of cement.
If the amount is less than 3 parts, a sufficient effect of accelerating the setting may not be obtained.
【００１２】ここでセメントとしては、普通、早強、超
早強、低熱、及び中庸熱等の各種ポルトランドセメン
ト、これらポルトランドセメントに、シリカや高炉スラ
グなどのポゾラン物質を混合した各種混合セメント、並
びに、アルミナセメントなどが挙げられる。As the cement, various types of Portland cements, such as ordinary, fast, super fast, low heat and moderate heat, various mixed cements obtained by mixing these portland cements with pozzolanic substances such as silica and blast furnace slag, and , Alumina cement and the like.
【００１３】水の使用量は特に限定されるものではな
く、通常の範囲が使用される。具体的には、水／セメン
ト組成物比25〜70％が好ましく、30〜60％がより好まし
い。25％未満では充分な作業性が得られない場合があ
り、70％を超えると充分な強度発現性が得られない場合
がある。[0013] The amount of water used is not particularly limited, and a normal range is used. Specifically, the water / cement composition ratio is preferably 25 to 70%, more preferably 30 to 60%. If it is less than 25%, sufficient workability may not be obtained, and if it exceeds 70%, sufficient strength may not be obtained.
【００１４】本発明のセメント組成物を使用したセメン
ト混練物の養生方法は、特に限定されるものではなく、
一般に行われている養生方法が可能である。また、混練
方法も、一般に用いられる方法でよく、特に限定される
ものではない。The method for curing a cement kneaded material using the cement composition of the present invention is not particularly limited.
General curing methods are possible. The kneading method may be a commonly used method, and is not particularly limited.
【００１５】本急結剤又は本発明のセメント組成物製造
時に使用する混合装置としては、既存のいかなる攪拌装
置も使用可能であり、例えば、傾胴ミキサ、オムニミキ
サ、Ｖ型ミキサ、ヘンシェルミキサ、及びナウタミキサ
などが使用可能である。また、混合はそれぞれの材料を
施工時に混合してもよいし、あらかじめ一部を、あるい
は全部を混合しておいても差し支えない。As the quick-setting agent or the mixing device used for producing the cement composition of the present invention, any existing stirring device can be used. For example, a tilting mixer, an omni mixer, a V-type mixer, a Henschel mixer, and A Nauta mixer or the like can be used. In addition, the mixing may be performed by mixing the respective materials at the time of construction, or a part or all of them may be mixed in advance.
【００１６】本急結剤は、湿式法、乾式法のいずれの吹
付工法にも適用可能である。The quick-setting agent can be applied to any of a wet method and a dry method.
【００１７】本発明では、セメントと本急結剤の他に、
砂や砂利等の骨材、補強繊維材、減水剤、高性能減水
剤、高性能ＡＥ減水剤、増粘剤、セメント膨張材、防錆
剤、防凍剤、ベントナイトやモンモリロナイトなどの粘
土鉱物、並びに、ゼオライト、ハイドロタルサイト、及
びハイドロカルマイトなどのイオン交換体等を本発明の
目的を実質的に阻害しない範囲で併用することが可能で
ある。In the present invention, in addition to the cement and the quick setting agent,
Aggregates such as sand and gravel, reinforcing fiber materials, water reducers, high performance water reducers, high performance AE water reducers, thickeners, cement expanders, rust inhibitors, antifreeze agents, clay minerals such as bentonite and montmorillonite, and , A zeolite, a hydrotalcite, and an ion exchanger such as hydrocalumite can be used together within a range that does not substantially inhibit the object of the present invention.
【００１８】[0018]
【実施例】以下、実験例により本発明を詳細に説明す
る。Hereinafter, the present invention will be described in detail with reference to experimental examples.
【００１９】実験例１ 表１に示す４Ａ族化合物、ＣＡ類、及びCa化合物類を
配合して本急結剤を調製した。セメント100部、砂300
部、及び水60部を混練してモルタルを調製した後、調製
した本急結剤７部を添加して10秒間混練し混練物を作製
し、その凝結時間を測定した。結果を表１に併記する。
比較のため４Ａ族化合物として市販の二酸化チタンを使
用して同様の実験を行った。結果を表１に併記する。Experimental Example 1 The quick-setting agent was prepared by blending a Group 4A compound, CAs and Ca compounds shown in Table 1. 100 parts cement, 300 sand
And 60 parts of water were kneaded to prepare a mortar, then 7 parts of the prepared quick-setting agent was added and kneaded for 10 seconds to produce a kneaded product, and the setting time was measured. The results are also shown in Table 1.
For comparison, a similar experiment was performed using commercially available titanium dioxide as the Group 4A compound. The results are also shown in Table 1.
【００２０】＜使用材料＞ ４Ａ族化合物Ａ：硫酸チタニル、TiOSO4、市販品 ４Ａ族化合物Ｂ：硫酸チタニウム、Ti(SO4)2換算で25％
水溶液、試薬１級 ４Ａ族化合物Ｃ：四塩化チタニウム、試薬１級 ４Ａ族化合物Ｄ：三塩化チタニウム、試薬１級 ４Ａ族化合物Ｅ：硫酸ジルコニウム４水和物、Zr(SO4)2
・4H2O、試薬１級 ４Ａ族化合物Ｆ：四塩化ジルコニウム、試薬１級 ４Ａ族化合物Ｇ：二塩化酸化ジルコニウム８水和物、試
薬１級 ４Ａ族化合物Ｈ：三塩化ジルコニウム、試薬１級 ４Ａ族化合物Ｉ：４Ａ族化合物Ａ50部と４Ａ族化合物Ｂ
50部の混合物 ４Ａ族化合物Ｊ：４Ａ族化合物Ａ50部と４Ａ族化合物Ｅ
50部の混合物 ４Ａ族化合物Ｋ：二酸化チタン、市販品 ＣＡ類 ：非晶質C12A7、試薬１級の炭酸カルシウ
ム、酸化アルミニウム、及び二酸化ケイ素を用い、CaO
／Al2O3モル比が12／７でSiO2含有量が３％となるよう
に原料を配合し、電気炉で1,600℃で溶融後、急冷して
合成、ブレーン値5,500cm2/g Ca化合物類イ：水酸化カルシウム、市販品 Ca化合物類ロ：無水セッコウ、市販品 Ca化合物類ハ：硝酸カルシウム、市販品 Ca化合物類ニ：水酸化アルミニウム、市販品 Ca化合物類ホ：硫酸アルミニウム18水和物、市販品 Ca化合物類ヘ：硝酸アルミニウム、市販品 Ca化合物類ト：Ca化合物類イ50部とCa化合物類ホ50部の
等量混合物 セメント ：電気化学工業社製、普通ポルトランドセメ
ント 砂 ：新潟県姫川産、川砂、比重2.62<Materials Used> Group 4A compound A: titanyl sulfate, TiOSO 4 , commercial product Group 4A compound B: titanium sulfate, 25% in terms of Ti (SO 4 ) 2
Aqueous solution, reagent primary 4A group compound C: titanium tetrachloride, primary reagent 4A group compound D: titanium trichloride, primary reagent 4A group compound E: zirconium sulfate tetrahydrate, Zr (SO 4 ) 2
・ 4H 2 O, reagent primary 4A group compound F: zirconium tetrachloride, primary reagent 4A group compound G: zirconium dichloride octahydrate, primary reagent 4A group compound H: zirconium trichloride, primary reagent 4A Group I compound: 50 parts of Group 4A compound A and Group 4A compound B
50 parts mixture Group 4A compound J: Group 4A compound A 50 parts and Group 4A compound E
50 parts mixture Group 4A compound K: titanium dioxide, commercially available CAs: amorphous C 12 A 7 , reagent grade 1 calcium carbonate, aluminum oxide, and silicon dioxide
/ Al 2 O 3 Molar ratio is 12/7 and SiO 2 content is 3%. The raw materials are blended, melted in an electric furnace at 1600 ° C., quenched and synthesized, Blaine value 5,500 cm 2 / g Ca Compounds A: Calcium hydroxide, commercially available Ca compounds B: Anhydrite, Commercial products Ca compounds C: Calcium nitrate, Commercial products Ca compounds D: Aluminum hydroxide, Commercial products Ca compounds E: Aluminum sulfate 18 water Japanese product, commercially available Ca compounds F: aluminum nitrate, commercially available Ca compounds G: Equivalent mixture of 50 parts of Ca compounds A and 50 parts of Ca compounds E Cement: Ordinary Portland cement manufactured by Denki Kagaku Kogyo Co., Ltd. Sand: Himekawa, Niigata Prefecture, river sand, specific gravity 2.62
【００２１】＜測定方法＞ 凝結時間 ：ASTM C 403に準じて、混練物を迅速に型枠
に詰めプロクター貫入抵抗値を測定して凝結時間の始発
と終結を測定<Measurement method> Setting time: In accordance with ASTM C 403, the kneaded material is quickly packed in a mold and the penetration value of the proctor is measured to measure the start and end of the setting time.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実験例２ ４Ａ族化合物Ａ20部、表２に示すＣＡ類60部、及びCa化
合物類ト20部からなる本急結剤を使用したこと以外は実
験例１と同様に行った。結果を表２に併記する。EXPERIMENTAL EXAMPLE 2 The same procedure as in Experimental Example 1 was carried out except that this quick-setting binder was used, which consisted of 20 parts of Group 4A compound A, 60 parts of CAs shown in Table 2, and 20 parts of Ca compounds. The results are also shown in Table 2.
【００２４】＜使用材料＞ ＣＡ類 ：結晶質C12A7、試薬１級の炭酸カルシウ
ム、及び酸化アルミニウムを用い、CaO／Al2O3モル比が
12／７となるように原料を配合し、電気炉で1,400℃で
焼成する工程を２回繰り返して合成、ブレーン値5,500c
m2/g ＣＡ類 ：結晶質C3A、試薬１級の炭酸カルシウムと
酸化アルミニウムを用い、CaO／Al2O3モル比が３／１と
なるように原料を配合し、電気炉で1,400℃で焼成する
工程を２回繰り返して合成、ブレーン値5,500cm2/g<Materials Used> CAs: Using crystalline C 12 A 7 , reagent grade calcium carbonate and aluminum oxide, the molar ratio of CaO / Al 2 O 3 is
The raw materials were blended to make 12/7, and the process of firing at 1,400 ° C in an electric furnace was repeated twice to synthesize, with a Blaine value of 5,500 c
m 2 / g CAs: crystalline C 3 A, using reagent-grade calcium carbonate and aluminum oxide, blending the raw materials so that the molar ratio of CaO / Al 2 O 3 is 3/1, and using an electric furnace for 1,400 Synthesis by repeating the process of baking at ℃ 2 times, Blaine value 5,500cm 2 / g
【００２５】[0025]
【表２】 [Table 2]
【００２６】実験例３ 比較のために、市販されているアルカリを含有するセメ
ント急結剤と、４Ａ族化合物Ａ20部、ＣＡ類60部、及
びCa化合物類ト20部からなる本急結剤（実験No.1-19）
の性能比較を実験例１と同様に行った。結果を表３に示
す。EXPERIMENTAL EXAMPLE 3 For comparison, a commercially available alkali-containing cement quick setting agent and a quick setting agent comprising 20 parts of a 4A group compound A, 60 parts of CAs and 20 parts of Ca compounds ( Experiment No.1-19)
Was performed in the same manner as in Experimental Example 1. Table 3 shows the results.
【００２７】＜使用材料＞ 市販品α ：市販のセメント急結剤、アルカリ含有量17
％、主成分非晶質カルシウムアルミネート 市販品β ：市販のセメント急結剤、アルカリ含有量21
％、主成分結晶質カルシウムアルミネート<Material used> Commercially available product α: Commercially available cement quick setting agent, alkali content 17
%, Main component amorphous calcium aluminate Commercial product β: Commercial cement quick setting agent, alkali content 21
%, Main component crystalline calcium aluminate
【００２８】[0028]
【表３】 [Table 3]
【００２９】実験例４ ４Ａ族化合物Ａ20部、ＣＡ類60部、及びCa化合物類ト
20部からなる本急結剤を使用し、セメント100部に対す
る本急結剤の使用量を表４に示すように変化したこと以
外は実験例１と同様に行った。結果を表４に併記した。Experimental Example 4 20 parts of Group 4A compound A, 60 parts of CAs, and Ca compounds
The procedure was performed in the same manner as in Experimental Example 1 except that 20 parts of the quick-setting admixture was used and the amount of the quick-setting admixture was changed as shown in Table 4 with respect to 100 parts of cement. The results are shown in Table 4.
【００３０】[0030]
【表４】 [Table 4]
【００３１】[0031]
【発明の効果】本発明のセメント急結剤はアルカリフリ
ーであって、アルカリ骨材反応の懸念がなく、セメント
コンクリートの凝結硬化を促進せしめることができるな
どの効果を奏する。The cement quick setting agent of the present invention is alkali-free, and has effects such as being able to accelerate the setting and hardening of cement concrete without fear of alkali-aggregate reaction.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 光男 新潟県西頚城郡青海町大字青海2209番地 電気化学工業株式会社青海工場内 Ｆターム(参考） 2D055 BA06 DB00 KA05 KA08 LA10 4G012 MB08 MB11 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Mitsuo Takahashi 2209 Aomi, Aomi-cho, Nishikubiki-gun, Niigata F-term in the Aomi Plant of Denki Kagaku Kogyo Co., Ltd. 2D055 BA06 DB00 KA05 KA08 LA10 4G012 MB08 MB11
Claims (5)
アルミネート類とを含有してなるアルカリフリー急結
剤。1. An alkali-free quick-setting agent containing a soluble compound of a 4A group element and calcium aluminates.
ウムであることを特徴とする請求項１記載のアルカリフ
リー急結剤。2. The alkali-free setting agent according to claim 1, wherein the group 4A element is titanium or zirconium.
する請求項１又は２記載のアルカリフリー急結剤。3. The alkali-free quick-setting agent according to claim 1, wherein the group 4A element is tetravalent.
ルミニウム化合物を含有してなる請求項１〜３のうちの
一項記載のアルカリフリー急結剤。4. The alkali-free quick-setting agent according to claim 1, further comprising a calcium compound and / or an aluminum compound.
記載のアルカリフリー急結剤とを含有してなるセメント
組成物。5. A cement composition comprising a cement and the alkali-free quick-setting agent according to claim 1.
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