JPH08165156A - Cement dispersing agent composition - Google Patents
Cement dispersing agent compositionInfo
- Publication number
- JPH08165156A JPH08165156A JP5048797A JP4879793A JPH08165156A JP H08165156 A JPH08165156 A JP H08165156A JP 5048797 A JP5048797 A JP 5048797A JP 4879793 A JP4879793 A JP 4879793A JP H08165156 A JPH08165156 A JP H08165156A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- acrylic acid
- meth
- synthesis
- general formula
- 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.)
- Pending
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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はセメント混和剤用の分散
剤組成物、更に詳しくは、効果の持続性に優れかつ低起
泡性で分散力に優れたセメント分散剤組成物に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant composition for cement admixtures, and more particularly to a cement dispersant composition having excellent effect sustainability, low foaming property and excellent dispersibility. .
【０００２】[0002]
【従来の技術と課題】従来セメント分散剤としてはポリ
ナフタリンスルホネ−ト、ポリメラミンスルホネ−ト、
リグニンスルホネ−トなどが使用されて来たが、これら
の化合物は分散効果が不十分であるばかりでなく、効果
の持続性即ちスランプロスに問題があり、業界の大きな
問題となって来た。2. Description of the Related Art Conventional cement dispersants include polynaphthalene sulfonate, polymelamine sulfonate,
Although lignin sulfonate and the like have been used, these compounds not only have insufficient dispersion effect but also have a problem of persistence of effect, that is, slump loss, which has become a major problem in the industry. .
【０００３】このような問題点を解決するためにポリカ
ルボン酸系の分散剤が提案されるようになり、たとえ
ば、特公昭５８−３８３８０の如くポリエチレングリコ
−ルモノアリルエ−テルとポリオキシエチレンポリオキ
シプロピレングリコ−ルマレイン酸エステル、またはマ
レイン酸のアルカリ金属塩、および(メタ)アクリル酸の
アルコ−ルエステルなどの共重合体、特開昭６２−２１
６９５０の如く(メタ)アクリル酸のポリエチレン(プロ
ピレン)グリコ−ルエステル、(メタ)アクリル(アルキレ
ンまたはヒドロキシアルキレン)スルホン酸塩、(メタ)
アクリル酸塩などの共重合体、特開平−２２６７５７の
如く(メタ)アクリル酸塩、(メタ)アクリルスルホン酸
塩、ポリエチレングリコ−ル(アルキルエ−テル)または
ポリプロピレングリコ−ル(アルキルエ−テル)の共重合
体、特公平−４０６２３の如く(メタ)アクリル酸アミ
ド、(メタ)アクリル酸塩、アクリロニトリルまたはアク
リル酸エステルまたはスチレンの共重合体、特開昭６２
−３０６４８の如く(メタ)アクリル酸アミドアルキルス
ルホネ−ト、(メタ)アクリル酸塩、アクリロニトリルま
たはアクリル酸エステルまたはスチレンの共重合体、特
開昭６２−２１２２５３及び特開昭６２−２１２２５２
の如く(メタ)アクリル酸アルキル(ヒドロキシアルキル)
スルホネ−ト、(メタ)アクリル酸塩、アクリロニトリル
またはアクリル酸エステルまたはスチレンの共重合体、
特開昭５９−１６２１５７の如く(メチルまたはフェニ
ル)アクリル酸のポリオキシエチレンまたはポリオキシ
ププロピレングリコ−ルのエステル、(メタ)アクリル酸
塩またはそのエステルの共重合体、特開昭５９−１９５
５６５の如く(メチル)アクリル酸またはアミドのポリオ
キシエチレンまたはポリオキシププロピレングリコ−ル
のエステル(エ−テル)、(メタ)アクリル酸塩の共重合体
などがあるが、いずれも製品の安定性、分散性能、低起
泡性、経済性などを全て満足するものはなく、業界の大
きな課題となってきている。本発明者らはかかる従来の
セメント分散剤の問題点を解決すべく鋭意研究の結果、
本発明に到達したものである。In order to solve these problems, polycarboxylic acid type dispersants have been proposed. For example, as disclosed in Japanese Patent Publication No. 58-38380, polyethylene glycol monoallyl ether and polyoxyethylene polyoxypropylene. Copolymers of glycol maleic acid ester or alkali metal salt of maleic acid, and alcohol ester of (meth) acrylic acid, and the like, JP-A-62-21
6950 such as polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) acrylic (alkylene or hydroxyalkylene) sulfonate, (meth)
A copolymer such as an acrylate, a (meth) acrylate, a (meth) acrylic sulfonate, a polyethylene glycol (alkyl ether) or a polypropylene glycol (alkyl ether) as described in JP-A-226757. Copolymer, (meth) acrylic acid amide, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer as disclosed in JP-B-40623, JP-A-62-62
Like (meth) acrylic acid amide alkyl sulfonate, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer as disclosed in JP-A-62-212253 and JP-A-62-212252.
Like alkyl (meth) acrylate (hydroxyalkyl)
Sulfonate, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer,
As disclosed in JP-A-59-162157, an ester of (methyl or phenyl) acrylic acid of polyoxyethylene or polyoxypropylene glycol, a (meth) acrylic acid salt or a copolymer of the ester, JP-A-59-195.
As shown in 565, there are poly (methyl) acrylic acid or amide polyoxyethylene or polyoxypropylene glycol ester (ether), (meth) acrylic acid copolymer, etc. There are no products that satisfy all of the requirements for water resistance, dispersion performance, low foaming property, economy, etc., and this has become a major issue for the industry. As a result of earnest research to solve the problems of the conventional cement dispersants, the present inventors have
The present invention has been reached.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は新規なセ
メント分散剤組成物として、一般式(１)にて示される化
合物That is, the present invention provides a novel cement dispersant composition containing a compound represented by the general formula (1):
【化４】 (但しＲは水素原子、またはメチル基、Ｍは一価のアル
カリ金属、アルカノ−ルアンモニウム)を０〜２０％、
一般式(２)にて示される化合物[Chemical 4] (However, R is a hydrogen atom or a methyl group, M is a monovalent alkali metal, alkanol ammonium) 0 to 20%,
Compound represented by general formula (2)
【化５】(但しxは５〜３０の整数、yは１〜５の整数、
Ｒ′はプロピレンまたはブチレン基)を１０〜８０％ 一般式(３)にて示される化合物(Where x is an integer of 5 to 30, y is an integer of 1 to 5,
R'is propylene or butylene group) 10 to 80% Compound represented by the general formula (3)
【化６】(但しｚは０または１、Ｒは水素原子、または
メチル基、Ｍは一価のアルカリ金属、アルカノ−ルアン
モニウム)を１０〜７０％の割合で共重合した水溶性共
重合体を主成分とするセメント分散剤組成物を提案する
ものである。Embedded image (wherein z is 0 or 1, R is a hydrogen atom or a methyl group, M is a monovalent alkali metal or alkanolammonium) in a proportion of 10 to 70%. A cement dispersant composition containing as a main component is proposed.
【０００５】本発明において使用される一般式(１)に示
される化合物はアクリル酸、メタアクリル酸のナトリウ
ム、カリウム、アンモニウム、モノまたはジまたはトリ
エタノルアミン塩を挙げることができるが性能及び経済
性の面からはナトリウム及びトリエタノ−ルアミンが好
ましい。Examples of the compound represented by the general formula (1) used in the present invention include sodium, potassium, ammonium, mono-, di- or triethanolamine salts of acrylic acid and methacrylic acid. From the aspect, sodium and triethanolamine are preferable.
【０００６】本発明において使用される一般式(２)に示
される化合物はメタアクリル酸またはアクリル酸にエチ
レンオキサイドを５から３０モル付加した後プロピレン
オキサイドまたはブチレンオキサイドを１〜５モル付加
することによって得られるが、性能上エチレンオキサイ
ドを８〜１５モル付加した後プロピレンオキサイドを２
〜４モルかまたはブチレンオキサイドを１から２モル付
加させた化合物が好ましい。一般式(２)の化合物は本発
明の根幹をなすものであって、先行の特許出願に見られ
る如くエチレンオキサイドのみを付加したものや、エチ
レンオキサイドとプロピレンオキサイドとをランダムに
付加したものは起泡性が高い点で問題があり、またプロ
ピレンオキサイドやブチレンオキサイドのみを付加した
場合は製品の安定性が悪く、また十分な分散性がないと
いう欠点を有している。また先にプロピレンオキサイド
を付加し次にエチレンオキサイドを付加したものは起泡
性の面で問題があり、本発明の対象とはならないもので
あり、かかる点については先行特許に全く開示されてい
ないものである。The compound represented by the general formula (2) used in the present invention is obtained by adding 5 to 30 mol of ethylene oxide to methacrylic acid or acrylic acid and then adding 1 to 5 mol of propylene oxide or butylene oxide. Although obtained, in terms of performance, after adding 8 to 15 mol of ethylene oxide, propylene oxide is added to 2
Compounds having -4 mol or 1 to 2 mol of butylene oxide added are preferred. The compound of the general formula (2) forms the basis of the present invention, and as shown in the prior patent application, a compound to which only ethylene oxide is added, or a compound to which ethylene oxide and propylene oxide are added at random occurs. There is a problem in that the foamability is high, and when only propylene oxide or butylene oxide is added, the stability of the product is poor and there is a drawback that the dispersibility is not sufficient. Further, the one in which propylene oxide is first added and then ethylene oxide is added has a problem in foaming property and is not the subject of the present invention, and such a point is not disclosed at all in the prior patent. It is a thing.
【０００７】本発明において使用される一般式(３)に示
される化合物はビニルスルホン酸、アリルスルホン酸、
メタリルスルホン酸、等のナトリウム、トリエタノ−ル
アミン塩が挙げられる。一般式(１)、一般式(２)及び一
般式(３)を使用して水溶性共重合体を得る方法について
は従来公知の技術を応用することで容易に得ることが出
来るものである。かくして得られた本発明のセメント分
散剤組成物は安定した水溶液で、分散性に優れ、スラン
プロスが少なく、低起泡性であるので泡の持ち込みが少
なく、また製造の上でも反応が単純で原料も比較的安価
である。本発明のセメント分散剤組成物はセメントに対
し通常０．０５％〜２％使用される。The compound represented by the general formula (3) used in the present invention is vinyl sulfonic acid, allyl sulfonic acid,
Examples thereof include sodium and triethanolamine salts such as methallyl sulfonic acid. The method for obtaining the water-soluble copolymer by using the general formula (1), the general formula (2) and the general formula (3) can be easily obtained by applying a conventionally known technique. The thus-obtained cement dispersant composition of the present invention is a stable aqueous solution, has excellent dispersibility, has little slump loss, and has a low foaming property, so that it does not bring in bubbles, and the reaction is simple in production. Raw materials are also relatively inexpensive. The cement dispersant composition of the present invention is usually used in an amount of 0.05% to 2% with respect to cement.
【０００８】[0008]
【実施例】次に本発明を実施例で説明する。EXAMPLES The present invention will now be described with reference to examples.
【実施例１】 (メタアクリル酸１５ＥＯ２ＰＯの合成)加圧釜に２−ヒ
ドロキシエチルメタアクリレ−ト１３０ｇ(１モル)を仕
込み、ハイドロキノン０．４４ｇ，三フッ化硼素２.５
ｇを添加し、窒素ガス雰囲気で圧力０.５ｋｇ／ｃｍ2、
４０〜６０℃でエチレンオキサイド６１６ｇ(１４モル)
を５時間を要し圧入し後同温度で１時間熟成した。次ぎ
にプロピレンオキサイド１１６ｇ(２モル)を６時間を要
し圧入し後３時間熟成した。その後３０〜５０℃、３０
〜８０ｍｍＨｇで未反応のエチレンオキサイドとプロピ
レンオキサイドとを留去した後濾過した。本品について
は実施例１の合成に使用する。Example 1 (Synthesis of 15EO2PO Methacrylic Acid) 130 g (1 mol) of 2-hydroxyethyl methacrylate was charged into a pressure kettle, 0.44 g of hydroquinone and 2.5 of boron trifluoride were charged.
g in a nitrogen gas atmosphere at a pressure of 0.5 kg / cm 2 ,
616 g (14 mol) of ethylene oxide at 40-60 ° C
The mixture was pressed for 5 hours and then aged at the same temperature for 1 hour. Next, 116 g (2 mol) of propylene oxide was injected under pressure for 6 hours and then aged for 3 hours. After that, 30 to 50 ℃, 30
Unreacted ethylene oxide and propylene oxide were distilled off at -80 mmHg and then filtered. This product is used in the synthesis of Example 1.
【０００９】(実施例１の合成)温度計、撹拌機、滴下ロ
−ト、窒素導入管、還流冷却器を付き四つ口フラスコに
蒸留水４２８ｇを仕込み、撹拌しながら窒素雰囲気中で
９０℃に昇温しメタアクリル酸１４ＥＯ２ＰＯ１７０
ｇ、メタアクリル酸１０ｇ、ビニルスルホン酸５２ｇ、
２５％苛性ソ−ダ １８ｇ、チオグリコ−ル酸アンモニ
ウム５０％水溶液９ｇ、過硫酸アンモニウム５％液 ９
０ｇを２時間を要し添加した。次ぎに９５℃で４時間反
応を行ない、固形分３０％、黄褐色透明液状の重合物８
４１ｇを得た。本品については後記のテストを行なう。(Synthesis of Example 1) 428 g of distilled water was charged into a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, and stirred at 90 ° C. in a nitrogen atmosphere. Temperature rises to 14 methacrylic acid 14EO2PO170
g, methacrylic acid 10 g, vinyl sulfonic acid 52 g,
25% caustic soda 18 g, ammonium thioglycolate 50% aqueous solution 9 g, ammonium persulfate 5% solution 9
0 g was added over 2 hours. Then, the reaction was carried out at 95 ° C. for 4 hours to obtain a yellowish brown transparent liquid polymer 8 having a solid content of 30%.
41 g was obtained. Perform the following test for this product.
【００１０】[0010]
【実施例２〜６】実施例１と同様に表１の如く合成し実
施例２〜７を得た。本品は何れも黄褐色透明液状であっ
た。本品については後記のテストを行なう。Examples 2 to 6 Examples 2 to 7 were obtained by synthesizing as shown in Table 1 in the same manner as in Example 1. This product was a yellowish brown transparent liquid. Perform the following test for this product.
【表１】 [Table 1]
【００１１】[0011]
【比較例１〜３】 (メタアクリル酸１５ＥＯの合成)先のメタアクリル酸１
５ＥＯ２ＰＯの合成においてＥＯを１４モル付加した時
点で冷却し未反応のエチレンオキサイドを留去し濾過し
メタアクリル酸１５ＥＯを得た。本品については比較例
１の合成に使用する。[Comparative Examples 1 to 3] (Synthesis of methacrylic acid 15EO) Previous methacrylic acid 1
In the synthesis of 5EO2PO, when 14 mol of EO was added, the mixture was cooled, unreacted ethylene oxide was distilled off, and filtered to obtain 15EO of methacrylic acid. This product is used in the synthesis of Comparative Example 1.
【００１２】(メタアクリル酸ランダム１５ＥＯ２ＰＯ
の合成)同様にエチレンオキサイドに代えエチレンオキ
サイド１４モルとプロピレンオキサイド２モルとを混合
し反応を行ない未反応のエチレンオキサイドとプロピレ
ンオキサイドとを留去し濾過しメタアクリル酸ランダム
１５ＥＯ２ＰＯを得た。本品については比較例２の合成
に使用する。(Random methacrylic acid 15EO2PO
Similarly, in place of ethylene oxide, 14 mol of ethylene oxide and 2 mol of propylene oxide were mixed to carry out a reaction, and unreacted ethylene oxide and propylene oxide were distilled off and filtered to obtain methacrylic acid random 15EO2PO. This product is used in the synthesis of Comparative Example 2.
【００１３】(アクリル酸１５ＰＯの合成)アクリル酸に
同様にプロピレンオキサイド１５モルを反応させアクリ
ル酸１５ＰＯを得た。本品については比較例３の合成に
使用する。(Synthesis of acrylic acid 15PO) Acrylic acid 15PO was obtained by similarly reacting 15 mol of propylene oxide with acrylic acid. This product is used for the synthesis of Comparative Example 3.
【００１４】(メタアクリル酸２ＰＯ１５ＥＯの合成)先
のメタアクリル酸１５ＥＯ２ＰＯの合成において、先ず
プロピレンオキサイドを反応せしめてから次ぎにエチレ
ンオキサイドを反応させメタアクリル酸２ＰＯ１５ＥＯ
を得た。本品については比較例４の合成に使用する。(Synthesis of methacrylic acid 2PO15EO) In the above-mentioned synthesis of methacrylic acid 15PO2PO, propylene oxide was first reacted and then ethylene oxide was reacted, followed by methacrylic acid 2PO15EO.
I got This product is used for the synthesis of Comparative Example 4.
【００１５】(比較例１〜４の合成)実施例１と同様に比
較例１〜３の合成を表２の如く行なった。比較例１及び
２は黄褐色透明液状であったが、比較例３は褐色で二層
に分離した。本品については後記のテストを行なう。(Synthesis of Comparative Examples 1 to 4) Synthesis of Comparative Examples 1 to 3 was carried out as shown in Table 2 in the same manner as in Example 1. Comparative Examples 1 and 2 were yellowish brown transparent liquids, whereas Comparative Example 3 was brown and separated into two layers. Perform the following test for this product.
【００１６】[0016]
【表２】 [Table 2]
【００１７】 セメント分散試験 セメント 普通ポルトランドセメント(比重３.１７) ３２０ kg/cm3 細骨剤 川砂 (比重２.５６) ８６７ kg/cm3 粗骨剤 川砂利 (比重２.５８) ９４７ kg/cm3 水 １７６ kg/cm3 の配合割合でコンクリ−トを調製した場合のスランプが
１８±１cmとなるように、実施例１〜７、比較例１〜
３、の添加量を求め、その時の空気量、スランプ、圧縮
強度及びその経時変化を測定した。Cement dispersion test Cement Normal Portland cement (specific gravity 3.17) 320 kg / cm3 Fine bone agent Kawasuna (specific gravity 2.56) 867 kg / cm3 Coarse Bone Agent River Gravel (Specific Gravity 2.58) 947 kg / cm3 Water 176 kg / cm3 The slump when the concrete is prepared in the mixing ratio of
Examples 1 to 7 and Comparative Examples 1 to 18 of 1 cm
Calculate the amount of addition of 3, and the air amount at that time, slump, compression
The strength and its change with time were measured.
【００１８】測定は空気量はＪＩＳ Ａ１１６，スラン
プはＪＩＳ Ａ１１０１，圧縮強度はＪＩＳ Ａ１１０
８の方法に準じ行なった。結果を表３に示すが本発明の
実施例１から７は何れも初期流動性に優れており、経時
安定性も良好でかつ空気量も少なく、きわめて優れたセ
メント分散性を示した。比較例１〜２及び４は分散性は
良好であるが空気量が多く、また比較例３は分散性が劣
っていた。The amount of air is measured according to JIS A116, the slump is measured according to JIS A1101, and the compressive strength is measured according to JIS A110.
The procedure of 8 was followed. The results are shown in Table 3, and in Examples 1 to 7 of the present invention, all had excellent initial fluidity, good stability over time, and a small amount of air, and exhibited extremely excellent cement dispersibility. In Comparative Examples 1 to 2 and 4, the dispersibility was good, but the air content was large, and in Comparative Example 3, the dispersibility was poor.
【００１９】[0019]
【表３】 [Table 3]
【００１９】[0019]
【発明の効果】本発明の分散剤は、実施例に見るように
初期流動性に優れており、経時安定性も良好でかつ空気
量も少なく、きわめて優れたセメント分散性を示した。EFFECTS OF THE INVENTION The dispersant of the present invention has excellent initial fluidity, good stability over time, and a small amount of air, as shown in the examples, and exhibits extremely excellent cement dispersibility.
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【手続補正書】[Procedure amendment]
【提出日】平成５年８月１１日[Submission date] August 11, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明はセメント混和剤用の分散
剤組成物、更に詳しくは、効果の持続性に優れかつ低起
泡性で分散力に優れたセメント分散剤組成物に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersant composition for cement admixtures, and more particularly to a cement dispersant composition having excellent effect sustainability, low foaming property and excellent dispersibility. .
【０００２】[0002]
【従来の技術と課題】従来セメント分散剤としてはポリ
ナフタリンスルホネ−ト、ポリメラミンスルホネ−ト、
リグニンスルホネ−トなどが使用されて来たが、これら
の化合物は分散効果が不十分であるばかりでなく、効果
の持続性即ちスランプロスに問題があり、業界の大きな
問題となって来た。2. Description of the Related Art Conventional cement dispersants include polynaphthalene sulfonate, polymelamine sulfonate,
Although lignin sulfonate and the like have been used, these compounds not only have insufficient dispersion effect but also have a problem of persistence of effect, that is, slump loss, which has become a major problem in the industry. .
【０００３】このような問題点を解決するためにポリカ
ルボン酸系の分散剤が提案されるようになり、たとえ
ば、特公昭５８−３８３８０の如くポリエチレングリコ
−ルモノアリルエ−テルとポリオキシエチレンポリオキ
シプロピレングリコ−ルマレイン酸エステル、またはマ
レイン酸のアルカリ金属塩、および(メタ)アクリル酸の
アルコ−ルエステルなどの共重合体、特開昭６２−２１
６９５０の如く(メタ)アクリル酸のポリエチレン(プロ
ピレン)グリコ−ルエステル、(メタ)アクリル(アルキレ
ンまたはヒドロキシアルキレン)スルホン酸塩、(メタ)
アクリル酸塩などの共重合体、特開平−２２６７５７の
如く(メタ)アクリル酸塩、(メタ)アクリルスルホン酸
塩、ポリエチレングリコ−ル(アルキルエ−テル)または
ポリプロピレングリコ−ル(アルキルエ−テル)の共重合
体、特公平−４０６２３の如く(メタ)アクリル酸アミ
ド、(メタ)アクリル酸塩、アクリロニトリルまたはアク
リル酸エステルまたはスチレンの共重合体、特開昭６２
−３０６４８の如く(メタ)アクリル酸アミドアルキルス
ルホネ−ト、(メタ)アクリル酸塩、アクリロニトリルま
たはアクリル酸エステルまたはスチレンの共重合体、特
開昭６２−２１２２５３及び特開昭６２−２１２２５２
の如く(メタ)アクリル酸アルキル(ヒドロキシアルキル)
スルホネ−ト、(メタ)アクリル酸塩、アクリロニトリル
またはアクリル酸エステルまたはスチレンの共重合体、
特開昭５９−１６２１５７の如く(メチルまたはフェニ
ル)アクリル酸のポリオキシエチレンまたはポリオキシ
ププロピレングリコ−ルのエステル、(メタ)アクリル酸
塩またはそのエステルの共重合体、特開昭５９−１９５
５６５の如く(メチル)アクリル酸またはアミドのポリオ
キシエチレンまたはポリオキシププロピレングリコ−ル
のエステル(エ−テル)、(メタ)アクリル酸塩の共重合体
などがあるが、いずれも製品の安定性、分散性能、低起
泡性、経済性などを全て満足するものはなく、業界の大
きな課題となってきている。本発明者らはかかる従来の
セメント分散剤の問題点を解決すべく鋭意研究の結果、
本発明に到達したものである。In order to solve such problems, polycarboxylic acid type dispersants have been proposed. For example, as disclosed in Japanese Patent Publication No. 58-38380, polyethylene glycol monoallyl ether and polyoxyethylene polyoxypropylene. Copolymers of glycol maleic acid ester or alkali metal salt of maleic acid, and alcohol ester of (meth) acrylic acid, and the like, JP-A-62-21
6950 such as polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) acrylic (alkylene or hydroxyalkylene) sulfonate, (meth)
A copolymer such as an acrylate, a (meth) acrylate, a (meth) acrylic sulfonate, a polyethylene glycol (alkyl ether) or a polypropylene glycol (alkyl ether) as described in JP-A-226757. Copolymer, (meth) acrylic acid amide, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer as disclosed in JP-B-40623, JP-A-62-62
Like (meth) acrylic acid amide alkyl sulfonate, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer as disclosed in JP-A-62-212253 and JP-A-62-212252.
Like alkyl (meth) acrylate (hydroxyalkyl)
Sulfonate, (meth) acrylic acid salt, acrylonitrile or acrylic acid ester or styrene copolymer,
As disclosed in JP-A-59-162157, an ester of (methyl or phenyl) acrylic acid of polyoxyethylene or polyoxypropylene glycol, a (meth) acrylic acid salt or a copolymer of the ester, JP-A-59-195.
As shown in 565, there are poly (methyl) acrylic acid or amide polyoxyethylene or polyoxypropylene glycol ester (ether), (meth) acrylic acid copolymer, etc. There are no products that satisfy all of the requirements for water resistance, dispersion performance, low foaming property, economy, etc., and this has become a major issue for the industry. As a result of earnest research to solve the problems of the conventional cement dispersants, the present inventors have
The present invention has been reached.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は新規なセ
メント分散剤組成物として、一般式(１)にて示される化
合物That is, the present invention provides a novel cement dispersant composition containing a compound represented by the general formula (1):
【化４】 (但しＲは水素原子、またはメチル基、Ｍは一価のアル
カリ金属、アルカノ−ルアンモニウム)を０〜２０％、
一般式(２)にて示される化合物[Chemical 4] (However, R is a hydrogen atom or a methyl group, M is a monovalent alkali metal, alkanol ammonium) 0 to 20%,
Compound represented by general formula (2)
【化５】 (但しxは５〜３０の整数、yは１〜５の整数、Ｒ′はプ
ロピレンまたはブチレン基)を１０〜８０％ 一般式(３)にて示される化合物Embedded image (Where x is an integer of 5 to 30, y is an integer of 1 to 5 and R'is a propylene or butylene group) 10 to 80% Compound represented by the general formula (3)
【化６】 (但しｚは０または１、Ｒは水素原子、またはメチル
基、Ｍは一価のアルカリ金属、アルカノ−ルアンモニウ
ム)を１０〜７０％の割合で共重合した水溶性共重合体
を主成分とするセメント分散剤組成物を提案するもので
ある。[Chemical 6] (Provided that z is 0 or 1, R is a hydrogen atom or a methyl group, M is a monovalent alkali metal, alkanolammonium) in a proportion of 10 to 70% as a main component of a water-soluble copolymer. A cement dispersant composition is proposed.
【０００５】本発明において使用される一般式(１)に示
される化合物はアクリル酸、メタアクリル酸のナトリウ
ム、カリウム、アンモニウム、モノまたはジまたはトリ
エタノルアミン塩を挙げることができるが性能及び経済
性の面からはナトリウム及びトリエタノ−ルアミンが好
ましい。Examples of the compound represented by the general formula (1) used in the present invention include sodium, potassium, ammonium, mono-, di- or triethanolamine salts of acrylic acid and methacrylic acid. From the aspect, sodium and triethanolamine are preferable.
【０００６】本発明において使用される一般式(２)に示
される化合物はメタアクリル酸またはアクリル酸にエチ
レンオキサイドを５から３０モル付加した後プロピレン
オキサイドまたはブチレンオキサイドを１〜５モル付加
することによって得られるが、性能上エチレンオキサイ
ドを８〜１５モル付加した後プロピレンオキサイドを２
〜４モルかまたはブチレンオキサイドを１から２モル付
加させた化合物が好ましい。一般式(２)の化合物は本発
明の根幹をなすものであって、先行の特許出願に見られ
る如くエチレンオキサイドのみを付加したものや、エチ
レンオキサイドとプロピレンオキサイドとをランダムに
付加したものは起泡性が高い点で問題があり、またプロ
ピレンオキサイドやブチレンオキサイドのみを付加した
場合は製品の安定性が悪く、また十分な分散性がないと
いう欠点を有している。また先にプロピレンオキサイド
を付加し次にエチレンオキサイドを付加したものは起泡
性の面で問題があり、本発明の対象とはならないもので
あり、かかる点については先行特許に全く開示されてい
ないものである。The compound represented by the general formula (2) used in the present invention is obtained by adding 5 to 30 mol of ethylene oxide to methacrylic acid or acrylic acid and then adding 1 to 5 mol of propylene oxide or butylene oxide. Although obtained, in terms of performance, after adding 8 to 15 mol of ethylene oxide, propylene oxide is added to 2
Compounds having -4 mol or 1 to 2 mol of butylene oxide added are preferred. The compound of the general formula (2) forms the basis of the present invention, and as shown in the prior patent application, a compound to which only ethylene oxide is added, or a compound to which ethylene oxide and propylene oxide are added at random occurs. There is a problem in that the foamability is high, and when only propylene oxide or butylene oxide is added, the stability of the product is poor and there is a drawback that the dispersibility is not sufficient. Further, the one in which propylene oxide is first added and then ethylene oxide is added has a problem in foaming property and is not the subject of the present invention, and such a point is not disclosed at all in the prior patent. It is a thing.
【０００７】本発明において使用される一般式(３)に示
される化合物はビニルスルホン酸、アリルスルホン酸、
メタリルスルホン酸、等のナトリウム、トリエタノ−ル
アミン塩が挙げられる。一般式(１)、一般式(２)及び一
般式(３)を使用して水溶性共重合体を得る方法について
は従来公知の技術を応用することで容易に得ることが出
来るものである。かくして得られた本発明のセメント分
散剤組成物は安定した水溶液で、分散性に優れ、スラン
プロスが少なく、低起泡性であるので泡の持ち込みが少
なく、また製造の上でも反応が単純で原料も比較的安価
である。本発明のセメント分散剤組成物はセメントに対
し通常０．０５％〜２％使用される。The compound represented by the general formula (3) used in the present invention is vinyl sulfonic acid, allyl sulfonic acid,
Examples thereof include sodium and triethanolamine salts such as methallyl sulfonic acid. The method for obtaining the water-soluble copolymer by using the general formula (1), the general formula (2) and the general formula (3) can be easily obtained by applying a conventionally known technique. The thus-obtained cement dispersant composition of the present invention is a stable aqueous solution, has excellent dispersibility, has little slump loss, and has a low foaming property, so that it does not bring in bubbles, and the reaction is simple in production. Raw materials are also relatively inexpensive. The cement dispersant composition of the present invention is usually used in an amount of 0.05% to 2% with respect to cement.
【０００８】[0008]
【実施例】次に本発明を実施例で説明する。EXAMPLES The present invention will now be described with reference to examples.
【実施例１】 (メタアクリル酸１５ＥＯ２ＰＯの合成)加圧釜に２−ヒ
ドロキシエチルメタアクリレ−ト１３０ｇ(１モル)を仕
込み、ハイドロキノン０．４４ｇ，三フッ化硼素２.５
ｇを添加し、窒素ガス雰囲気で圧力０.５ｋｇ／ｃｍ2、
４０〜６０℃でエチレンオキサイド６１６ｇ(１４モル)
を５時間を要し圧入し後同温度で１時間熟成した。次ぎ
にプロピレンオキサイド１１６ｇ(２モル)を６時間を要
し圧入し後３時間熟成した。その後３０〜５０℃、３０
〜８０ｍｍＨｇで未反応のエチレンオキサイドとプロピ
レンオキサイドとを留去した後濾過した。本品について
は実施例１の合成に使用する。Example 1 (Synthesis of 15EO2PO Methacrylic Acid) 130 g (1 mol) of 2-hydroxyethyl methacrylate was charged into a pressure kettle, 0.44 g of hydroquinone and 2.5 of boron trifluoride were charged.
g in a nitrogen gas atmosphere at a pressure of 0.5 kg / cm 2 ,
616 g (14 mol) of ethylene oxide at 40-60 ° C
The mixture was pressed for 5 hours and then aged at the same temperature for 1 hour. Next, 116 g (2 mol) of propylene oxide was injected under pressure for 6 hours and then aged for 3 hours. After that, 30 to 50 ℃, 30
Unreacted ethylene oxide and propylene oxide were distilled off at -80 mmHg and then filtered. This product is used in the synthesis of Example 1.
【０００９】(実施例１の合成)温度計、撹拌機、滴下ロ
−ト、窒素導入管、還流冷却器を付き四つ口フラスコに
蒸留水４２８ｇを仕込み、撹拌しながら窒素雰囲気中で
９０℃に昇温しメタアクリル酸１４ＥＯ２ＰＯ１７０
ｇ、メタアクリル酸１０ｇ、ビニルスルホン酸５２ｇ、
２５％苛性ソ−ダ １８ｇ、チオグリコ−ル酸アンモニ
ウム５０％水溶液９ｇ、過硫酸アンモニウム５％液 ９
０ｇを２時間を要し添加した。次ぎに９５℃で４時間反
応を行ない、固形分３０％、黄褐色透明液状の重合物８
４１ｇを得た。本品については後記のテストを行なう。(Synthesis of Example 1) 428 g of distilled water was charged into a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser, and stirred at 90 ° C. in a nitrogen atmosphere. Temperature rises to 14 methacrylic acid 14EO2PO170
g, methacrylic acid 10 g, vinyl sulfonic acid 52 g,
25% caustic soda 18 g, ammonium thioglycolate 50% aqueous solution 9 g, ammonium persulfate 5% solution 9
0 g was added over 2 hours. Then, the reaction was carried out at 95 ° C. for 4 hours to obtain a yellowish brown transparent liquid polymer 8 having a solid content of 30%.
41 g was obtained. Perform the following test for this product.
【００１０】[0010]
【実施例２〜６】実施例１と同様に表１の如く合成し実
施例２〜７を得た。本品は何れも黄褐色透明液状であっ
た。本品については後記のテストを行なう。Examples 2 to 6 Examples 2 to 7 were obtained by synthesizing as shown in Table 1 in the same manner as in Example 1. This product was a yellowish brown transparent liquid. Perform the following test for this product.
【表１】 [Table 1]
【００１１】[0011]
【比較例１〜３】 (メタアクリル酸１５ＥＯの合成)先のメタアクリル酸１
５ＥＯ２ＰＯの合成においてＥＯを１４モル付加した時
点で冷却し未反応のエチレンオキサイドを留去し濾過し
メタアクリル酸１５ＥＯを得た。本品については比較例
１の合成に使用する。[Comparative Examples 1 to 3] (Synthesis of methacrylic acid 15EO) Previous methacrylic acid 1
In the synthesis of 5EO2PO, when 14 mol of EO was added, the mixture was cooled, unreacted ethylene oxide was distilled off, and filtered to obtain 15EO of methacrylic acid. This product is used in the synthesis of Comparative Example 1.
【００１２】(メタアクリル酸ランダム１５ＥＯ２ＰＯ
の合成)同様にエチレンオキサイドに代えエチレンオキ
サイド１４モルとプロピレンオキサイド２モルとを混合
し反応を行ない未反応のエチレンオキサイドとプロピレ
ンオキサイドとを留去し濾過しメタアクリル酸ランダム
１５ＥＯ２ＰＯを得た。本品については比較例２の合成
に使用する。(Random methacrylic acid 15EO2PO
Similarly, in place of ethylene oxide, 14 mol of ethylene oxide and 2 mol of propylene oxide were mixed to carry out a reaction, and unreacted ethylene oxide and propylene oxide were distilled off and filtered to obtain methacrylic acid random 15EO2PO. This product is used in the synthesis of Comparative Example 2.
【００１３】(アクリル酸１５ＰＯの合成)アクリル酸に
同様にプロピレンオキサイド１５モルを反応させアクリ
ル酸１５ＰＯを得た。本品については比較例３の合成に
使用する。(Synthesis of acrylic acid 15PO) Acrylic acid 15PO was obtained by similarly reacting 15 mol of propylene oxide with acrylic acid. This product is used for the synthesis of Comparative Example 3.
【００１４】(メタアクリル酸２ＰＯ１５ＥＯの合成)先
のメタアクリル酸１５ＥＯ２ＰＯの合成において、先ず
プロピレンオキサイドを反応せしめてから次ぎにエチレ
ンオキサイドを反応させメタアクリル酸２ＰＯ１５ＥＯ
を得た。本品については比較例４の合成に使用する。(Synthesis of methacrylic acid 2PO15EO) In the above-mentioned synthesis of methacrylic acid 15PO2PO, propylene oxide was first reacted and then ethylene oxide was reacted, followed by methacrylic acid 2PO15EO.
I got This product is used for the synthesis of Comparative Example 4.
【００１５】(比較例１〜４の合成)実施例１と同様に比
較例１〜３の合成を表２の如く行なった。比較例１及び
２は黄褐色透明液状であったが、比較例３は褐色で二層
に分離した。本品については後記のテストを行なう。(Synthesis of Comparative Examples 1 to 4) Synthesis of Comparative Examples 1 to 3 was carried out as shown in Table 2 in the same manner as in Example 1. Comparative Examples 1 and 2 were yellowish brown transparent liquids, whereas Comparative Example 3 was brown and separated into two layers. Perform the following test for this product.
【００１６】[0016]
【表２】 [Table 2]
【００１７】 セメント分散試験 セメント 普通ポルトランドセメント(比重３.１７) ３２０ kg/cm3 細骨剤 川砂 (比重２.５６) ８６７ kg/cm3 粗骨剤 川砂利 (比重２.５８) ９４７ kg/cm3 水 １７６ kg/cm3 の配合割合でコンクリ−トを調製した場合のスランプが
１８±１cmとなるように、実施例１〜７、比較例１〜
３、の添加量を求め、その時の空気量、スランプ、圧縮
強度及びその経時変化を測定した。Cement dispersion test Cement Normal Portland cement (specific gravity 3.17) 320 kg / cm 3 Fine bone agent Kawasuna (specific gravity 2.56) 867 kg / cm 3 Coarse bone agent Kawagravel (specific gravity 2.58) 947 kg / cm 3 Examples 1 to 7 and Comparative Examples 1 to 1 so that the slump when the concrete was prepared at a mixing ratio of water 176 kg / cm 3 was 18 ± 1 cm.
The addition amount of 3 was determined, and the air amount, slump, compressive strength and its change with time at that time were measured.
【００１８】測定は空気量はＪＩＳ Ａ１１６，スラン
プはＪＩＳ Ａ１１０１，圧縮強度はＪＩＳ Ａ１１０
８の方法に準じ行なった。結果を表３に示すが本発明の
実施例１から７は何れも初期流動性に優れており、経時
安定性も良好でかつ空気量も少なく、きわめて優れたセ
メント分散性を示した。比較例１〜２及び４は分散性は
良好であるが空気量が多く、また比較例３は分散性が劣
っていた。The amount of air is measured according to JIS A116, the slump is measured according to JIS A1101, and the compressive strength is measured according to JIS A110.
The procedure of 8 was followed. The results are shown in Table 3, and in Examples 1 to 7 of the present invention, all had excellent initial fluidity, good stability over time, and a small amount of air, and exhibited extremely excellent cement dispersibility. In Comparative Examples 1 to 2 and 4, the dispersibility was good, but the air content was large, and in Comparative Example 3, the dispersibility was poor.
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【発明の効果】本発明の分散剤は、実施例に見るように
初期流動性に優れており、経時安定性も良好でかつ空気
量も少なく、きわめて優れたセメント分散性を示した。EFFECTS OF THE INVENTION The dispersant of the present invention has excellent initial fluidity, good stability over time, and a small amount of air, as shown in the examples, and exhibits extremely excellent cement dispersibility.
Claims (1)
カリ金属、アルカノ−ルアンモニウムを示す）を０〜２
０％、一般式（２）にて示される化合物 【化２】 （但しxは５〜３０の整数、yは１〜５の整数、Ｒ′はプ
ロピレンまたはブチレン基をそれぞれ示す）を１０〜８
０％ 一般式（３）にて示される化合物 【化３】 （但しｚは０または１、Ｒは水素原子、またはメチル
基、Ｍは一価のアルカリ金属、アルカノ−ルアンモニウ
ムをそれぞれ示す）を１０〜７０％の割合で共重合した
水溶性共重合体を主成分とするセメント分散剤組成物。1. A compound represented by the general formula (1): (Provided that R is a hydrogen atom or a methyl group, M is a monovalent alkali metal or alkanol ammonium)
0%, a compound represented by the general formula (2): (Provided that x is an integer of 5 to 30, y is an integer of 1 to 5, and R'represents a propylene or butylene group, respectively).
0% Compound represented by the general formula (3) (Wherein z is 0 or 1, R is a hydrogen atom, or a methyl group, M is a monovalent alkali metal or alkanol ammonium, respectively) in a proportion of 10 to 70%. A cement dispersant composition containing the main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5048797A JPH08165156A (en) | 1993-02-16 | 1993-02-16 | Cement dispersing agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5048797A JPH08165156A (en) | 1993-02-16 | 1993-02-16 | Cement dispersing agent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08165156A true JPH08165156A (en) | 1996-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5048797A Pending JPH08165156A (en) | 1993-02-16 | 1993-02-16 | Cement dispersing agent composition |
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| Country | Link |
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| JP (1) | JPH08165156A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850895A1 (en) * | 1996-12-26 | 1998-07-01 | Nippon Shokubai Co., Ltd. | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
| US6258162B1 (en) | 1998-10-22 | 2001-07-10 | Nippon Shokubai Co., Ltd. | Cement composition |
| US6310143B1 (en) | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| US7368488B2 (en) * | 2003-05-07 | 2008-05-06 | Nippon Shokubai Co., Ltd. | Cement admixture and cement admixture composite |
-
1993
- 1993-02-16 JP JP5048797A patent/JPH08165156A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850895A1 (en) * | 1996-12-26 | 1998-07-01 | Nippon Shokubai Co., Ltd. | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
| US6174980B1 (en) | 1996-12-26 | 2001-01-16 | Nippon Shokubai Co., Ltd. | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition |
| EP1118598A2 (en) * | 1996-12-26 | 2001-07-25 | Nippon Shokubai Co., Ltd. | Cement dispersant and cement composition |
| US6388038B1 (en) | 1996-12-26 | 2002-05-14 | Nippon Shokubai Co., Ltd. | Method for producing polycarboxylic acid for cement dispersant and cement composition |
| EP1118598A3 (en) * | 1996-12-26 | 2004-05-12 | Nippon Shokubai Co., Ltd. | Cement dispersant and cement composition |
| EP2256097A3 (en) * | 1996-12-26 | 2011-03-16 | Nippon Shokubai Co., Ltd. | Cement dispersant, method for preparation of said dispersant and cement composition |
| US6258162B1 (en) | 1998-10-22 | 2001-07-10 | Nippon Shokubai Co., Ltd. | Cement composition |
| US6310143B1 (en) | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| US7368488B2 (en) * | 2003-05-07 | 2008-05-06 | Nippon Shokubai Co., Ltd. | Cement admixture and cement admixture composite |
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