JPH10226550A - Additive composition for cement - Google Patents

Additive composition for cement

Info

Publication number
JPH10226550A
JPH10226550A JP9026241A JP2624197A JPH10226550A JP H10226550 A JPH10226550 A JP H10226550A JP 9026241 A JP9026241 A JP 9026241A JP 2624197 A JP2624197 A JP 2624197A JP H10226550 A JPH10226550 A JP H10226550A
Authority
JP
Japan
Prior art keywords
cement
acid
additive composition
compound
group
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
Application number
JP9026241A
Other languages
Japanese (ja)
Other versions
JP3896620B2 (en
Inventor
Seigo Kinoshita
誠吾 木下
Susumu Honda
進 本多
Akinori Ito
昭則 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NOF Corp
Original Assignee
NOF Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NOF Corp filed Critical NOF Corp
Priority to JP02624197A priority Critical patent/JP3896620B2/en
Publication of JPH10226550A publication Critical patent/JPH10226550A/en
Application granted granted Critical
Publication of JP3896620B2 publication Critical patent/JP3896620B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/062—Microsilica, e.g. colloïdal silica
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1022—Non-macromolecular 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain an additive compsn. for cement capable of easily regulating the amt. of air entrained in the case of use in a dry cement blend such as premixed mortar and having high strength exhibiting property at the time of curing by absorbing a specified polyoxyalkylene compd. in fine porous silica powder. SOLUTION: A polyoxyalkylene compd. represented by the formula is absorbed in fine porous silica powder having 50-400m<2> /g BET specific surface area and <=30μm average particle diameter by the Coulter counter method to obtain the objective additive compsn. In the formula, Z is a residue of a compd. having 1-8 active H atoms, each of A<1> O and A<2> O is one or more kinds of 2-4C oxyalkylene groups, in the case of two or more groups, the groups may be in a block added or random added state, each of R<1> and R<2> is H, 1-22C hydrocarbon or acyl, 0<=a<=150, 0<=b<=150, a+b>=1, m>=0, n>=0 and 1<=m+n<=8.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は粉末状のセメント用
添加剤組成物に関する。さらに詳しくは、プレミックス
モルタル等の乾燥セメント配合物に添加することによ
り、連行空気量の調整を容易にし、かつ強度発現性の高
い粉末状のセメント用添加剤組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery additive composition for cement. More specifically, the present invention relates to a powdery cement additive composition which is easy to adjust the amount of entrained air by adding to a dry cement composition such as a premix mortar and has high strength.

【０００２】[0002]

【従来の技術】現在、コンクリ−ト、モルタル等のセメ
ント配合物の練り混ぜ時における連行空気の過剰混入に
よる構造物、成型品等の圧縮強度低下、外観上の品質低
下等を防止するためにシリコーン系、ポリアルキレング
リコール系等の公知の消泡剤が用いられている。これら
の消泡剤の添加量は必要に応じて最適化されるが、ほと
んどの場合においてその添加量は、使用するセメントに
対して０．５重量％以下であり、そのため通常は消泡剤
を単独で使用することはなく、流動性改善あるいは高耐
久性化、高強度化等を目的として添加される液状のセメ
ント用添加剤である減水剤、高性能減水剤、ＡＥ減水
剤、高性能ＡＥ減水剤、流動化剤等にあらかじめ添加し
て用いられることが多い。2. Description of the Related Art At present, in order to prevent a decrease in the compressive strength of a structure or a molded product due to excessive entrainment of air at the time of kneading a cement compound such as a concrete or a mortar, and a quality deterioration in appearance. Known antifoaming agents such as silicone type and polyalkylene glycol type are used. The amount of addition of these defoamers is optimized as required, but in most cases the amount is not more than 0.5% by weight, based on the cement used, so that usually the defoamer is A water-reducing agent, a high-performance water-reducing agent, an AE water-reducing agent, a high-performance AE, which is a liquid cement additive added for the purpose of improving fluidity, increasing durability, increasing strength, etc., without using it alone It is often used by adding it in advance to a water reducing agent, a fluidizing agent, or the like.

【０００３】しかし消泡剤をセメント用添加剤にあらか
じめ添加した場合、本来、消泡剤は水に溶けにくいた
め、その保存状態によっては消泡剤成分だけが分離して
くることがあり、所望の性能が得られないという問題を
生じていた。この問題を解決するために、特開平８−１
６５１５７号公報では、減水剤成分と消泡剤成分の混合
物に特殊な界面活性剤を添加する方法が開示されてい
る。しかしこの方法は、通常のレディミクストコンクリ
ート工場あるいはコンクリート二次製品工場においては
適用できるものの、界面活性剤が液状品であるために乾
燥セメント配合物には適用できなかった。また、乾燥セ
メント配合物においても連行空気量の調整のために消泡
剤が用いられることがあるが、その場合も消泡剤の添加
量は微量で、均一に混合することは容易ではなかった。
そこで、乾燥セメント配合物に用いる材料と混合しても
連行空気量の調整と強度発現性が十分に発揮でき、貯蔵
安定性に優れた粉末状の消泡剤の開発が望まれていた。[0003] However, when an antifoaming agent is added to a cement additive in advance, the antifoaming agent is inherently hardly soluble in water, so that only the antifoaming component may be separated depending on the storage condition. However, there has been a problem that the performance of the above cannot be obtained. In order to solve this problem, Japanese Patent Application Laid-Open No.
No. 65157 discloses a method of adding a special surfactant to a mixture of a water reducing agent component and an antifoaming agent component. However, although this method can be applied in ordinary ready-mixed concrete factories or secondary concrete product factories, it cannot be applied to dry cement formulations because the surfactant is a liquid product. In addition, even in a dry cement composition, an antifoaming agent may be used for adjusting the amount of entrained air, but in this case, the addition amount of the antifoaming agent is very small, and it is not easy to mix uniformly. .
Therefore, it has been desired to develop a powdery defoaming agent which can sufficiently control the amount of entrained air and exhibit sufficient strength even when mixed with a material used for a dry cement composition and has excellent storage stability.

【０００４】粉末状消泡剤としては特公平１−３４０８
８号公報に、比表面積が１５０ｍ2／ｇ以上、平均粒子
径が１００μｍ以上、嵩比重が１５０ｇ／Ｌ以上の粉末
状シリカにシリコーン系、ポリエーテル変性シリコーン
系またはポリアルキレングリコール系の消泡剤を吸着さ
せた組成が開示されている。しかしこれらの粉末状消泡
剤はセメント配合物等の土木建築分野用に開発されたも
のでなく、セメント配合物に用いても連行空気量の調整
あるいはその経時安定性において性能的に満足できるも
のでなかった。また一方で、セメント配合物用に開発さ
れた粉末状のセメント用添加剤としては、特公平７−６
４６０７号公報に開示されているが、このものは硬化セ
メント配合物の乾燥収縮低減を目的としたもので、連行
空気量の調整においては性能的に満足できるものではな
かった。[0004] As a powdery defoaming agent, JP-B 1-3408
No. 8 discloses powdery silica having a specific surface area of at least 150 m 2 / g, an average particle diameter of at least 100 μm, a bulk specific gravity of at least 150 g / L, and a silicone-based, polyether-modified silicone-based or polyalkylene glycol-based defoaming agent. Is disclosed. However, these powdered defoamers have not been developed for use in the field of civil engineering and construction, such as cement compounds. Even when used in cement compounds, they are satisfactory in terms of adjusting the amount of entrained air or their temporal stability. Was not. On the other hand, as a powdery cement additive developed for a cement compound, JP-B-7-6
Although it is disclosed in Japanese Patent No. 4607, it is intended to reduce the drying shrinkage of the hardened cement composition, and is not satisfactory in terms of performance in adjusting the amount of entrained air.

【０００５】[0005]

【発明が解決しようとする課題】本発明は、上記のよう
な従来技術の欠点を改善し、セメント用添加剤としてプ
レミックスモルタル等の乾燥セメント配合物に用いた場
合、連行空気量を容易に調整することができ、かつ、硬
化したときの強度発現性が高い新規なセメント用添加剤
組成物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention improves the above-mentioned drawbacks of the prior art and, when used in a dry cement formulation such as premix mortar as a cement additive, can easily reduce the amount of entrained air. An object of the present invention is to provide a novel additive composition for cement that can be adjusted and has high strength development when cured.

【０００６】[0006]

【課題を解決するための手段】本発明は、下記の一般式
［１］で示されるポリオキシアルキレン化合物を、ＢＥ
Ｔ法による比表面積が５０〜４００ｍ2／ｇ、コールタ
ーカウンター法による平均粒子径が３０μｍ以下である
多孔質シリカ微粉末にあらかじめ吸収させてなる粉末状
のセメント用添加剤組成物である。According to the present invention, a polyoxyalkylene compound represented by the following general formula [1] is converted to BE
This is a powdery cement additive composition which is previously absorbed in porous silica fine powder having a specific surface area of 50 to 400 m 2 / g by T method and an average particle diameter of 30 μm or less by Coulter counter method.

【０００７】[0007]

【化２】 Embedded image

【０００８】（ただし、Ｚは１〜８個の活性水素原子を
有する化合物の残基、Ａ1ＯおよびＡ2Ｏはそれぞれ１種
又は２種以上の炭素数２〜４のオキシアルキレン基で、
２種以上のときはブロック状に付加していてもランダム
状に付加していてもよく、Ｒ1およびＲ2はそれぞれ水素
原子、炭素数１〜２２の炭化水素基またはアシル基、０
≦ａ≦１５０、０≦ｂ≦１５０、ａ＋ｂ≧１、ｍ≧０、
ｎ≧０および１≦ｍ＋ｎ≦８である。）(Where Z is a residue of a compound having 1 to 8 active hydrogen atoms, A 1 O and A 2 O are one or two or more oxyalkylene groups having 2 to 4 carbon atoms, respectively)
When two or more kinds are used, they may be added in block form or in random form, and R 1 and R 2 each represent a hydrogen atom, a hydrocarbon group or an acyl group having 1 to 22 carbon atoms,
≦ a ≦ 150, 0 ≦ b ≦ 150, a + b ≧ 1, m ≧ 0,
n ≧ 0 and 1 ≦ m + n ≦ 8. )

【０００９】[0009]

【発明の実施の形態】一般式［１］において、Ｚは１〜
８個の活性水素原子を有する化合物の残基である。１〜
８個の活性水素原子を有する化合物としては、水酸基ま
たはアミノ基もしくはイミノ基を有する化合物が挙げら
れる。水酸基を有する化合物としては、たとえば、炭素
数１〜２２の１価アルコール；カテコール、レゾルシ
ン、ヒドロキノン、フロログルシン等の多価フェノー
ル；エチレングリコール、プロピレングリコール、ブチ
レングリコール、テトラメチレングリコール、ドデシレ
ングリコール、オクタデシレングリコール、ネオペンチ
ルグリコール、スチレングリコール、グリセリン、ジグ
リセリン、ポリグリセリン、トリメチロールエタン、ト
リメチロールプロパン、１，３，５−ペンタントリオー
ル、エリスリトール、ペンタエリスリトール、ジペンタ
エリスリトール、ソルビトール、ソルビド、ソルビトー
ル−グリセリン縮合物、アドニトール、アラビトール、
キシリトール、マンニトール等の多価アルコール；トリ
エタノールアミン、トリイソプロパノールアミン等のア
ルカノールアミン；キシロース、アラビノース、リボー
ス、ラムノース、グルコース、フルクトース、ガラクト
ース、マンノース、ソルボース、セロビオース、マルト
ース、イドマルトース、トレハロース、シュクロース等
の糖、さらにこれらの部分エーテル化物やエステル化物
等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the general formula [1], Z is 1 to
It is the residue of a compound having eight active hydrogen atoms. 1 to
Examples of the compound having eight active hydrogen atoms include a compound having a hydroxyl group, an amino group, or an imino group. Examples of the compound having a hydroxyl group include monohydric alcohols having 1 to 22 carbon atoms; polyhydric phenols such as catechol, resorcin, hydroquinone, and phloroglucin; ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, dodecylene glycol; Octadecylene glycol, neopentyl glycol, styrene glycol, glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbide, Sorbitol-glycerin condensate, adonitol, arabitol,
Polyhydric alcohols such as xylitol and mannitol; alkanolamines such as triethanolamine and triisopropanolamine; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, idmaltose, trehalose, sucrose And partially etherified and esterified products thereof.

【００１０】アミノ基またはイミノ基を有する化合物と
しては、メチルアミン、ジメチルアミン、エチルアミ
ン、ジエチルアミン、プロピルアミン、ブチルアミン、
ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オ
クチルアミン、ノニルアミン、デシルアミン、ドデシル
アミン等のモノアミン；エチレンジアミン、テトラメチ
レンジアミン、ヘキサメチレンジアミン等のジアミン；
ジエチレントリアミン、トリエチレンテトラミン等のポ
リアミン；アニリン、Ｎ−メチルアニリン、トルイジン
等の芳香族アミン；アミングリシン、アラニン、バリ
ン、ロイシン、フェニルアラニン、セリン、チロシン、
アスパラギン酸、グルタミン酸等のアミノ酸等が挙げら
れる。水酸基とアミノ基とを有する化合物としてはエタ
ノールアミン、ジエタノールアミンがある。Examples of the compound having an amino group or an imino group include methylamine, dimethylamine, ethylamine, diethylamine, propylamine, butylamine,
Monoamines such as pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine and dodecylamine; diamines such as ethylenediamine, tetramethylenediamine and hexamethylenediamine;
Polyamines such as diethylenetriamine and triethylenetetramine; aromatic amines such as aniline, N-methylaniline and toluidine; amine glycine, alanine, valine, leucine, phenylalanine, serine, tyrosine;
Amino acids such as aspartic acid and glutamic acid; Examples of the compound having a hydroxyl group and an amino group include ethanolamine and diethanolamine.

【００１１】Ａ1ＯおよびＡ2Ｏはそれぞれ炭素数２〜４
のオキシアルキレン基で、それらは１種または２種以上
の混合物であってもよい。付加重合の形はランダム状付
加あるいはブロック状付加のどちらでもよいが、ブロッ
ク状付加が好ましい。消泡効果の点からオキシエチレン
基の含有量は４０モル％以下が好ましい。A 1 O and A 2 O each have 2 to 4 carbon atoms.
And they may be one kind or a mixture of two or more kinds. The form of the addition polymerization may be either random addition or block addition, but block addition is preferred. The content of the oxyethylene group is preferably 40 mol% or less from the viewpoint of the defoaming effect.

【００１２】Ｒ1およびＲ2は、水素原子、炭素数１〜２
２の炭化水素基またはアシル基である。炭化水素基とし
ては、たとえば、メチル基、エチル基、プロピル基、イ
ソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチ
ル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル
基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチ
ル基、２−エチルヘキシル基、ノニル基、デシル基、ウ
ンデシル基、ドデシル基、イソトリデシル基、テトラデ
シル基、ヘキサデシル基、オクタデシル基、イソオクタ
デシル基、ノナデシル基、エイコシル基、ドコシル基、
オレイル基、オクチルドデシル基、ベヘニル基、シクロ
ヘキシル基、ベンジル基、クレジル基、ブチルフェニル
基、オクチルフェニル基、ノニルフェニル基、ドデシル
フェニル基等の脂肪族飽和炭化水素基、不飽和炭化水素
基、脂環式炭化水素基、芳香族炭化水素基、置換芳香族
炭化水素基等が挙げられる。またアシル基としてはギ
酸、酢酸、プロピオン酸、酪酸、イソ酪酸、カプロン
酸、カプリル酸、ウンデシレン酸、ラウリン酸、ミリス
チン酸、マルガリン酸、ステアリン酸、アラキン酸、ベ
ヘニン酸、パルミトレイン酸、オレイン酸、リノール
酸、リノレン酸、エルカ酸、イソパルチミン酸、イソス
テアリン酸、安息香酸等に由来する直鎖または分岐の飽
和アシル基や不飽和アシル基、芳香族アシル基等が挙げ
られる。R 1 and R 2 each represent a hydrogen atom, a carbon number of 1 to 2;
2 hydrocarbon groups or acyl groups. Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, and heptyl. Octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, isooctadecyl, nonadecyl, eicosyl, docosyl,
Aliphatic saturated hydrocarbon groups such as oleyl group, octyldodecyl group, behenyl group, cyclohexyl group, benzyl group, cresyl group, butylphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, unsaturated hydrocarbon groups, and fatty acids Examples include a cyclic hydrocarbon group, an aromatic hydrocarbon group, and a substituted aromatic hydrocarbon group. As the acyl group, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, caprylic acid, undecylenic acid, lauric acid, myristic acid, margaric acid, stearic acid, arachiic acid, behenic acid, palmitoleic acid, oleic acid, Examples thereof include a linear or branched saturated acyl group, unsaturated acyl group, aromatic acyl group and the like derived from linoleic acid, linolenic acid, erucic acid, isopartic acid, isostearic acid, benzoic acid and the like.

【００１３】本発明において、Ｒ1およびＲ2で表される
炭化水素基またはアシル基の炭素数が２２を超えても、
特に消泡作用に悪影響を及ぼすことはないが、原料入手
が困難となるので２２までが好ましい。ａおよびｂはそ
れぞれ０〜１５０で、ａ＋ｂ≧１である。ａおよびｂが
１５０を超えると、粘度が高くなり製造が困難となる。
ａ＋ｂが０であると消泡効果を示さない。ｍ≧０、ｎ≧
０、１≦ｍ＋ｎ≦８である。製造性の点からａｍ＋ｂｎ
の値は、１０〜３００であることが好ましい。In the present invention, even if the hydrocarbon group or acyl group represented by R 1 and R 2 has more than 22 carbon atoms,
In particular, it does not adversely affect the defoaming action, but it is difficult to obtain a raw material, so that up to 22 is preferable. a and b are each 0 to 150, and a + b ≧ 1. When a and b exceed 150, the viscosity becomes high and the production becomes difficult.
When a + b is 0, no defoaming effect is exhibited. m ≧ 0, n ≧
0, 1 ≦ m + n ≦ 8. Am + bn from the viewpoint of manufacturability
Is preferably 10 to 300.

【００１４】本発明において、一般式［１］で示される
ポリオキシアルキレン化合物の製造法については特に制
限はないが、たとえば、活性水素原子を酸素原子または
窒素原子上に有する活性水素化合物に、エチレンオキシ
ド、プロピレンオキシドまたはブチレンオキシドをラン
ダム状あるいはブロック状に付加させることによって得
ることができ、さらに遊離の水酸基の水素原子の一部ま
たは全部を、公知の方法により炭化水素基またはアシル
基により置換することによって得ることができる。In the present invention, there is no particular limitation on the method for producing the polyoxyalkylene compound represented by the general formula [1]. For example, an active hydrogen compound having an active hydrogen atom on an oxygen atom or a nitrogen atom may be replaced with ethylene oxide. Can be obtained by adding propylene oxide or butylene oxide in random or block form, and further substituting a part or all of the hydrogen atoms of a free hydroxyl group with a hydrocarbon group or an acyl group by a known method. Can be obtained by

【００１５】本発明に用いる多孔質シリカ微粉末として
は、一般に含水珪酸、湿式シリカ、乾式シリカ、合成シ
リカと呼ばれているものを使用することができる。本発
明に用いるシリカの化学的性質としては非晶質の二酸化
ケイ素含有量９０％以上で、物理的性質としてはＢＥＴ
法による比表面積が５０〜４００ｍ2／ｇ、コールター
カウンター法による平均粒子径が３０μｍ以下、好まし
くは２０μｍ以下のものが挙げられる。比表面積が５０
ｍ2／ｇより小さいと、消泡剤成分を多量に含有するこ
とができず、４００ｍ2／ｇより大きいとその供給性に
問題が生じる。平均粒子径が３０μｍより大きくなる
と、強度の発現性が低下する。本発明のセメント用添加
剤組成物におけるポリオキシアルキレン化合物と多孔質
シリカ微粉末の配合割合は、多孔質シリカ微粉末の物理
的性質によっても異なるが、一般にシリカ１００重量部
に対して５〜２００重量部でポリオキシアルキレン化合
物を吸収させて使用することが好ましい。５重量部より
少ないと、トータルとして添加するセメント用添加剤組
成物が多くなってしまうので、セメント配合物の硬化前
後の物性に悪影響を及ぼす恐れがあるので好ましくな
く、２００重量部を越えると、保存状態によっては凝集
およびケ−キングが起こることがあり、作業性が悪くな
ったり、セメント用添加剤としての性能が低下すること
があるので好ましくない。またポリオキシアルキレン化
合物を多孔質シリカに吸収させるときの形状は、液状で
ある必要があり、そのものの物性に応じて加温して粘性
を低くした後、多孔質シリカ微粉末に吸収させてもよ
い。As the porous silica fine powder used in the present invention, those generally called hydrated silica, wet silica, dry silica and synthetic silica can be used. The silica used in the present invention has a chemical property of 90% or more of amorphous silicon dioxide and a physical property of BET.
Specific surface area by the method is 50 to 400 m 2 / g, and average particle diameter by the Coulter counter method is 30 μm or less, preferably 20 μm or less. Specific surface area is 50
If it is less than m 2 / g, a large amount of the defoamer component cannot be contained, and if it is more than 400 m 2 / g, there is a problem in its supply. When the average particle diameter is larger than 30 μm, the strength developability decreases. The mixing ratio of the polyoxyalkylene compound and the porous silica fine powder in the cement additive composition of the present invention varies depending on the physical properties of the porous silica fine powder, but generally ranges from 5 to 200 parts per 100 parts by weight of silica. It is preferable that the polyoxyalkylene compound is absorbed and used in parts by weight. If the amount is less than 5 parts by weight, the total amount of the cement additive composition to be added becomes large, which may adversely affect the physical properties of the cement composition before and after curing. Depending on the storage state, coagulation and caking may occur, resulting in poor workability and poor performance as an additive for cement. In addition, the shape when the polyoxyalkylene compound is absorbed by the porous silica must be in a liquid state, and after being heated to reduce the viscosity according to the physical properties of the compound, the porous silica fine powder may be absorbed. Good.

【００１６】前記ポリオキシアルキレン化合物を多孔質
シリカ微粉末に吸収させる方法としては、例えば、ナウ
タ−ミキサ、ヘンシェルミキサ等の混合撹拌機で両者を
混練する方法が挙げられる。混練する際の温度は、ポリ
オキシアルキレン化合物の物性に応じて異なるが、加温
下、冷却下または室温下のいずれの場合を採用してもよ
い。また、混練する際の雰囲気は、不活性ガス存在下あ
るいは大気中であってもよい。上記の方法で処理した多
孔質シリカ微粉末は、そのままセメント用添加剤として
使用することができるが、さらに遠心ミル等の粉砕機で
微粉砕した後、分粒機を通して、混練の際に凝集した多
孔質シリカを再微粉化して供することがより好ましい。As a method of absorbing the polyoxyalkylene compound into the fine porous silica powder, for example, a method of kneading both with a mixing stirrer such as a Nauta-mixer or a Henschel mixer may be mentioned. The temperature at the time of kneading varies depending on the physical properties of the polyoxyalkylene compound, but any of heating, cooling or room temperature may be employed. The atmosphere for kneading may be in the presence of an inert gas or in the air. The porous silica fine powder treated by the above method can be used as it is as an additive for cement, but after further finely pulverizing with a pulverizer such as a centrifugal mill, agglomerated during kneading through a particle sizer. It is more preferable that the porous silica be re-pulverized and provided.

【００１７】本発明のセメント用添加剤組成物の添加量
は、通常、セメントに対してセメント用添加剤組成物中
のポリオキシアルキレン化合物として０．０００１〜
０．５重量％であることが好ましく、０．０００５〜
０．３重量％であることがより好ましい。セメント用添
加剤組成物中のポリオキシアルキレン化合物の添加量が
０．０００１重量％未満であると、本発明の効果である
連行空気量の調整が困難となり、０．５重量％を超えて
も本発明の効果がさらに改善されることはないので、経
済的に不利となる。The additive amount of the cement additive composition of the present invention is usually 0.0001 to 0.0001 as the polyoxyalkylene compound in the cement additive composition relative to the cement.
It is preferably 0.5% by weight,
More preferably, it is 0.3% by weight. When the addition amount of the polyoxyalkylene compound in the additive composition for cement is less than 0.0001% by weight, it is difficult to adjust the entrained air amount, which is an effect of the present invention, and even if it exceeds 0.5% by weight. Since the effect of the present invention is not further improved, it is economically disadvantageous.

【００１８】本発明のセメント用添加剤組成物を適用す
ることができるセメントとしては、普通ポルトランドセ
メント、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、中庸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等のポルトランドセメント、高炉セ
メント、シリカセメント、フライアッシュセメント等の
混合セメント、またはこれらのセメントと、高炉スラ
グ、フライアッシュ、シリカフューム、石灰石等の混和
材を組み合わせたセメント、さらにはビ−ライト系セメ
ント、油井セメント、高硫酸塩スラグセメント、アルミ
ナセメント、マグネシヤセメント、耐酸セメント等の特
殊セメントを挙げることができる。これらのセメントは
必要に応じて１種または２種以上組み合わせて用いるこ
とができる。本発明のセメント用添加剤組成物の使用方
法は、モルタルやコンクリ−トに使用するセメントにあ
らかじめ混合して使用することを基本とするが、水にあ
らかじめ分散・懸濁させたり、注水と同時に添加して使
用することもできる。Examples of the cement to which the additive composition for cement of the present invention can be applied include Portland cement such as ordinary Portland cement, early-strength Portland cement, ultra-high-strength Portland cement, moderately heated Portland cement, and sulfate-resistant Portland cement. Cement, such as cement, blast-furnace cement, silica cement, fly ash cement, or a combination of these cements and admixtures such as blast-furnace slag, fly ash, silica fume, limestone, and belite cement, oil well cement And special cements such as high sulfate slag cement, alumina cement, magnesium cement and acid-resistant cement. These cements can be used alone or in combination of two or more as needed. The method for using the additive composition for cement of the present invention is based on the fact that it is preliminarily mixed and used with cement used for mortar and concrete, but it is dispersed and suspended in water in advance or simultaneously with water injection. It can also be used by adding.

【００１９】本発明のセメント用添加剤組成物は、その
効果を損なわない程度で、必要に応じて他のセメント用
添加剤と併用して使用することも可能である。他のセメ
ント用添加剤の例としては、ナフタレンスルホン酸ホル
ムアルデヒド縮合物の塩、メラミンスルホン酸ホルムア
ルデヒド縮合物の塩、リグニンスルホン酸の塩、芳香族
アミノスルホン酸ホルムアルデヒド縮合物の塩、ポリカ
ルボン酸系等の他の減水剤、空気連行剤、分離低減剤、
凝結遅延剤、凝結促進剤、膨張材、乾燥収縮低減剤、防
錆剤等を挙げることができる。The cement additive composition of the present invention can be used in combination with other cement additives, if necessary, to the extent that its effect is not impaired. Examples of other cement additives include a salt of a naphthalenesulfonic acid formaldehyde condensate, a salt of a melaminesulfonic acid formaldehyde condensate, a salt of ligninsulfonic acid, a salt of an aromatic aminosulfonic acid formaldehyde condensate, and a polycarboxylic acid-based salt. Other water reducing agents, air entraining agents, separation reducing agents, etc.
Examples thereof include a setting retarder, a setting accelerator, an expanding material, a drying shrinkage reducing agent, and a rust preventive.

【００２０】[0020]

【実施例】以下、製造例、実施例および比較例を用いて
本発明を説明する。 製造例 第１表に示されるポリオキシアルキレン化合物と第２表
に示される多孔質シリカ微粉末を第３表に示した重量比
でヘンシェルミキサ（三井三池化工機(株)製）に投入
し、混合して本発明のセメント用添加剤組成物１〜８を
得た。また同様の操作で、第１表に示されるポリオキシ
アルキレン化合物［Ａ］と第２表に示される平均粒子径
が本発明の範囲を外れる「トクシールＵＲ」（(株)トク
ヤマ製）とを混合して比較用として組成物９を得た。組
成物１０については、第２表に示される比表面積が本発
明の範囲を外れる「マイクロシリカ＃９４０」（エルケ
ムジャパン(株)）が吸油性がないため、第１表に示され
るポリオキシアルキレン化合物［Ａ］と第２表に示され
る「マイクロシリカ＃９４０」とを混合せず組成のみを
示した。The present invention will be described below with reference to Production Examples, Examples and Comparative Examples. Production Example A polyoxyalkylene compound shown in Table 1 and a porous silica fine powder shown in Table 2 were charged into a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a weight ratio shown in Table 3; By mixing, additive compositions 1 to 8 for cement of the present invention were obtained. In a similar operation, the polyoxyalkylene compound [A] shown in Table 1 was mixed with “Tokusil UR” (manufactured by Tokuyama Corporation) having an average particle size shown in Table 2 which is out of the range of the present invention. Thus, composition 9 was obtained for comparison. As for the composition 10, "Microsilica # 940" (Elchem Japan Co., Ltd.) whose specific surface area shown in Table 2 is out of the range of the present invention has no oil absorbing property, and therefore the polyoxyalkylene shown in Table 1 is not used. Only the composition was shown without mixing the compound [A] and “Microsilica # 940” shown in Table 2.

【００２１】[0021]

【表１】 [Table 1]

【００２２】[0022]

【表２】 [Table 2]

【００２３】[0023]

【表３】 [Table 3]

【００２４】実施例１ 製造例で得られたセメント用添加剤組成物１をモルタル
試験に供し、性能評価を行った。モルタル試験に供した
材料は、セメント（普通ポルトランドセメント、比重
３．１６）、砂（千葉県君津産山砂、比重２．６０）、
および水（水道水）である。配合組成は、水セメント比
３３．０％、セメント砂比５８．５％で、１回の練り混
ぜ量は、セメント１，５００ｇ、砂２，５６３ｇ、高性
能ＡＥ減水剤「マリアリムＡＫＭ−２０Ｆ」（日本油脂
(株)製）１８．０ｇ、水４７７ｇおよびセメント用添加
剤組成物１５．０ｇ（セメント重量に対して外割で１．
０％、ポリオキシアルキレン化合物として０．１％）と
した。モルタルの練り混ぜは５リットルモルタルミキサ
（テスコ(株)製）を用い、セメント、セメント用添加剤
組成物１および砂をミキサに投入し１５秒間低速回転で
空練り行った後、水を加えて低速回転で１分間、さらに
高速回転で３分間練り混ぜた。そして、練り上がり直後
および６０分後の０打フロ−値（落下運動を加えない自
然に広がったモルタルの直径）および連行空気量を測定
した。測定方法操作はＪＩＳ Ｒ ５２０１に準じた。６
０分後の測定は、静置しておいたモルタルを測定前にヘ
ラで１０回練り返して行った。練り上がり直後の０打フ
ロ−は２６２ｍｍ、連行空気量は１．８％で、６０分後
の０打フロ−は２４２ｍｍ、連行空気量は１．９％であ
った。なお、試験時のモルタル温度は２０±１℃であっ
た。また、６０分後の測定後にモルタルをＪＩＳ Ｒ ５
２０１に準じて型枠（４０×４０×１６０ｍｍ）に詰め
供試体を作成した。７日後の圧縮強度を測定した結果、
６６．０ＭＰａであった。Example 1 The additive composition 1 for cement obtained in the production example was subjected to a mortar test to evaluate the performance. Materials used for the mortar test were cement (ordinary Portland cement, specific gravity 3.16), sand (mountain sand from Kimitsu, Chiba Prefecture, specific gravity 2.60),
And water (tap water). The composition is 33.0% of water cement ratio and 58.5% of cement sand ratio, and the mixing amount at one time is 1,500 g of cement, 2,563 g of sand, and high performance AE water reducing agent "Mariarim AKM-20F". (Japanese fats and oils
18.0 g, water 477 g, and an additive composition for cement 15.0 g (1.
0% and 0.1% as a polyoxyalkylene compound). The kneading of the mortar was performed using a 5-liter mortar mixer (manufactured by Tesco Corporation), and the cement, the additive composition for cement 1 and sand were charged into the mixer, kneaded at low speed for 15 seconds, and then water was added. The mixture was kneaded at low speed for 1 minute and further at high speed for 3 minutes. The 0-stroke flow value (diameter of the mortar that naturally spread without any falling motion) immediately after kneading and after 60 minutes, and the amount of entrained air were measured. The measuring method operation was in accordance with JIS R5201. 6
The measurement after 0 minutes was performed by kneading the mortar which had been left still ten times with a spatula before the measurement. The 0-stroke flow immediately after kneading was 262 mm and the entrained air amount was 1.8%, and the 0-stroke flow after 60 minutes was 242 mm and the entrained air amount was 1.9%. The mortar temperature during the test was 20 ± 1 ° C. After the measurement after 60 minutes, the mortar was JIS R5
According to 201, the test pieces were packed in a mold (40 × 40 × 160 mm). As a result of measuring the compressive strength after 7 days,
It was 66.0 MPa.

【００２５】[0025]

【表４】 [Table 4]

【００２６】実施例２〜９ 製造例で得られたセメント用添加剤組成物１〜８を実施
例１と同じ配合組成のモルタルに第４表に示す割合で添
加し、実施例１と同様の方法で試験を行った。試験結果
をまとめて第４表に示す。なお、試験時のモルタル温度
は２０±１℃であった。Examples 2 to 9 Additive compositions 1 to 8 for cement obtained in Production Examples were added to mortars having the same composition as in Example 1 at the ratios shown in Table 4 and the same results as in Example 1 were obtained. The method was tested. Table 4 summarizes the test results. The mortar temperature during the test was 20 ± 1 ° C.

【００２７】比較例１ 本発明のセメント用添加剤組成物の代わりに「カープレ
ックス＃８０」１３．５ｇを単独で用いた以外は実施例
１と同じ配合組成のモルタルで、実施例１と同様の方法
で試験を行った。試験結果を第４表に示す。なお、試験
時のモルタル温度は２０±１℃であった。Comparative Example 1 A mortar having the same composition as in Example 1 except that 13.5 g of “Carplex # 80” was used alone instead of the additive composition for cement of the present invention. The test was performed by the following method. Table 4 shows the test results. The mortar temperature during the test was 20 ± 1 ° C.

【００２８】比較例２ 本発明のセメント用添加剤組成物の代わりに、セメント
用添加剤組成物９を実施例１と同じ配合組成のモルタル
に、第４表に示す割合で添加し、実施例１と同様の方法
で試験を行った。試験結果を第４表に示す。なお、試験
時のモルタル温度は２０±１℃であった。Comparative Example 2 In place of the cement additive composition of the present invention, a cement additive composition 9 was added to a mortar having the same composition as in Example 1 at a ratio shown in Table 4. The test was performed in the same manner as in Example 1. Table 4 shows the test results. The mortar temperature during the test was 20 ± 1 ° C.

【００２９】比較例３ 本発明のセメント用添加剤組成物の代わりに、セメント
用添加剤組成物１０を実施例１と同じ配合組成のモルタ
ルに、第４表に示す割合で添加し、実施例１と同様の方
法で試験を行った。なお、「マイクロシリカ＃９４０」
は吸油性がないため、予めポリオキシアルキレン化合物
を吸収することなく、別々に計量して用いた。試験結果
を第４表に示す。なお、試験時のモルタル温度は２０±
１℃であった。Comparative Example 3 In place of the cement additive composition of the present invention, a cement additive composition 10 was added to a mortar having the same composition as in Example 1 at the ratio shown in Table 4. The test was performed in the same manner as in Example 1. In addition, "micro silica # 940"
Since they have no oil absorbency, they were separately measured and used without previously absorbing the polyoxyalkylene compound. Table 4 shows the test results. The mortar temperature during the test was 20 ±
1 ° C.

【００３０】第４表の結果より、実施例１〜９の本発明
のセメント用添加剤組成物は、比較例１〜３のセメント
用添加剤組成物に比べて、連行空気量の経時安定性が良
好で、強度発現性が高いことがわかる。すなわち比較例
１では、本発明のセメント用添加剤組成物の１成分であ
るポリオキシアルキレン化合物を用いていないために、
連行空気量が多くなり、その経時安定性も悪い。また、
連行空気量が多いことにより強度低下を招いている。比
較例２では、多孔質シリカ微粉末の平均粒子径が大きい
ものを使用すると、本発明の同程度の６０分後の連行空
気量を有する実施例１、２、４、５、８に比べて強度が
小さくなっている。比較例３では、消泡剤成分と比表面
積の小さいシリカフュームを別々に加えたものは連行空
気量の経時変化が大きく、強度発現も同程度の６０分後
の連行空気量を有する実施例７と比べて小さくなってい
る。From the results in Table 4, it can be seen that the additive compositions for cement of the present invention of Examples 1 to 9 are more stable than the additive compositions for cement of Comparative Examples 1 to 3 over time in the amount of entrained air. Is good and the strength development is high. That is, in Comparative Example 1, since the polyoxyalkylene compound, which is one component of the additive composition for cement of the present invention, was not used,
The amount of entrained air increases, and its stability over time is poor. Also,
A large amount of entrained air causes a decrease in strength. In Comparative Example 2, when the porous silica fine powder having a large average particle diameter was used, the fine particles were compared with Examples 1, 2, 4, 5, and 8 of the present invention having the same amount of entrained air after 60 minutes. Strength is reduced. In Comparative Example 3, when the antifoaming agent component and the silica fume having a small specific surface area were separately added, the amount of entrained air after 60 minutes was substantially the same as that of the entrained air, and the strength was substantially the same as that of Example 7 having the same amount of strength. It is smaller than that.

【００３１】[0031]

【発明の効果】本発明のセメント用添加剤組成物をプレ
ミックスモルタル等の乾燥セメント配合物に使用するこ
とにより、連行空気量の調整が容易で、しかもその経時
安定性が良好になる。さらには、硬化したセメント配合
物の強度発現性が高い。したがってセメント配合物の品
質改善、高強度化、高耐久性化が可能になる。By using the additive composition for cement of the present invention in a dry cement composition such as a premix mortar, the amount of entrained air can be easily adjusted and the stability over time can be improved. Furthermore, the hardened cementitious composition has high strength development. Therefore, it is possible to improve the quality, increase the strength, and increase the durability of the cement composition.

フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０８Ｇ 65/26 Ｃ０８Ｇ 65/26 Ｃ０４Ｂ 103:50 Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C08G 65/26 C08G 65/26 C04B 103: 50

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】下記の一般式［１］で示されるポリオキシ
アルキレン化合物を、ＢＥＴ法による比表面積が５０〜
４００ｍ2／ｇ、コールターカウンター法による平均粒
子径が３０μｍ以下である多孔質シリカ微粉末にあらか
じめ吸収させてなる粉末状のセメント用添加剤組成物。 【化１】 （ただし、Ｚは１〜８個の活性水素原子を有する化合物
の残基、Ａ1ＯおよびＡ2Ｏはそれぞれ１種または２種以
上の炭素数２〜４のオキシアルキレン基で、２種以上の
ときはブロック状に付加していてもランダム状に付加し
ていてもよく、Ｒ 1およびＲ2はそれぞれ水素原子、炭素
数１〜２２の炭化水素基またはアシル基、０≦ａ≦１５
０、０≦ｂ≦１５０、ａ＋ｂ≧１、ｍ≧０、ｎ≧０およ
び１≦ｍ＋ｎ≦８である。）1. A polyoxy compound represented by the following general formula [1]:
The alkylene compound has a specific surface area of 50 to 50 according to the BET method.
400mTwo/ G, average grain by Coulter counter method
For porous silica fine powder with a diameter of 30 μm or less
A powdery additive composition for cement, which is preliminarily absorbed. Embedded image(Where Z is a compound having 1 to 8 active hydrogen atoms)
Residue A1O and ATwoO is one or more of each
In the above oxyalkylene group having 2 to 4 carbon atoms, two or more
Sometimes, even if they are added in blocks, they are added in random
May be R 1And RTwoAre hydrogen and carbon, respectively
A hydrocarbon group or an acyl group represented by Formulas 1 to 22, 0 ≦ a ≦ 15
0, 0 ≦ b ≦ 150, a + b ≧ 1, m ≧ 0, n ≧ 0 and
And 1 ≦ m + n ≦ 8. )
JP02624197A 1997-02-10 1997-02-10 Additive composition for cement Expired - Fee Related JP3896620B2 (en)

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WO2000047533A1 (en) * 1999-02-10 2000-08-17 Degussa Construction Chemicals Gmbh Powdery polyethercarboxylate-based polymeric compositions
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JP2006232651A (en) * 2005-02-22 2006-09-07 Matsumoto Yushi Seiyaku Co Ltd Admixture for extrusion molding of cement and extrusion molded cement product
US7273524B2 (en) 2002-02-06 2007-09-25 Nippon Shokubai Co., Ltd. Concrete composition method of producing concrete compositions and cement admixture
WO2009015800A2 (en) * 2007-07-31 2009-02-05 Cognis Ip Management Gmbh Methods and compositions for improving air entrainment in cementitious mixtures
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JP2002536289A (en) * 1999-02-10 2002-10-29 デグサ コンストラクション ケミカルズ ゲゼルシャフト ミット ベシュレンクテル ハフツング Powdered polymer composition based on polyether carboxylate
EP1120384A1 (en) * 2000-01-27 2001-08-01 Wacker Polymer Systems GmbH & Co. KG Water repellant agent for hydrophobing building materials with gypsum binder
US7273524B2 (en) 2002-02-06 2007-09-25 Nippon Shokubai Co., Ltd. Concrete composition method of producing concrete compositions and cement admixture
JP2006232651A (en) * 2005-02-22 2006-09-07 Matsumoto Yushi Seiyaku Co Ltd Admixture for extrusion molding of cement and extrusion molded cement product
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WO2009015800A3 (en) * 2007-07-31 2009-04-02 Cognis Ip Man Gmbh Methods and compositions for improving air entrainment in cementitious mixtures
WO2009015800A2 (en) * 2007-07-31 2009-02-05 Cognis Ip Management Gmbh Methods and compositions for improving air entrainment in cementitious mixtures
WO2011148091A1 (en) * 2010-05-25 2011-12-01 Ciments Francais Superplastisticizer based on surface-modified mineral nanoparticles for mortar and concrete
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