JPWO2016067826A1 - Post-additive admixture for concrete - Google Patents
Post-additive admixture for concrete Download PDFInfo
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- JPWO2016067826A1 JPWO2016067826A1 JP2016532654A JP2016532654A JPWO2016067826A1 JP WO2016067826 A1 JPWO2016067826 A1 JP WO2016067826A1 JP 2016532654 A JP2016532654 A JP 2016532654A JP 2016532654 A JP2016532654 A JP 2016532654A JP WO2016067826 A1 JPWO2016067826 A1 JP WO2016067826A1
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- structural unit
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- concrete
- admixture
- Prior art date
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- Granted
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- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000016 octadecenoyl group Chemical group O=C([*])C([H])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28C7/00—Controlling the operation of apparatus for producing mixtures of clay or cement with other substances; Supplying or proportioning the ingredients for mixing clay or cement with other substances; Discharging the mixture
- B28C7/04—Supplying or proportioning the ingredients
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- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができるコンクリート用後添加混和剤を提供する。分子中に特定の２種の構成単位を必須の構成単位として有する共重合体の一つ又は二つ以上から成り、且つ全体の酢酸換算含有割合が０．１〜４．０質量％であるものをコンクリート用後添加混和剤として用いた。Provided is a post-additive for concrete which can be added to the prepared concrete which has not yet been solidified to maintain the fluidity of the concrete in a state immediately before the post-addition over a long period of time. Containing one or two or more copolymers having two specific structural units as essential structural units in the molecule, and having a total acetic acid equivalent content of 0.1 to 4.0% by mass Was used as a post-additive admixture for concrete.
Description
本発明はコンクリート用後添加混和剤に関する。各種材料を練り混ぜてコンクリートを調製し、調製したコンクリートを実際の使用場所まで運搬して、運搬したコンクリートを使用する場合、例えば運搬に長時間を要し、調製したコンクリートの流動性が低下して、使用し難くなることがある。このような場合、調製したまだ固まっていないコンクリートに混和剤を後添加して、コンクリートの流動性を保持することが行なわれる。本発明は、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができる後添加混和剤に関する。 The present invention relates to a post-additive admixture for concrete. When mixing concrete materials to prepare concrete, transporting the prepared concrete to the actual place of use and using the transported concrete, for example, it takes a long time to transport, and the fluidity of the prepared concrete decreases. May be difficult to use. In such a case, an admixture is post-added to the prepared concrete that has not yet solidified to maintain the fluidity of the concrete. The present invention relates to a post-added admixture that can maintain the fluidity of concrete over a long period of time in a state immediately before post-addition by post-adding to the prepared concrete that has not yet solidified.
コンクリートの流動性や流動保持性を向上するため、その調製時に、ナフタレン系、メラミン系、アミノスルホン酸系又はポリカルボン酸系等の各種の混和剤が使用されている（例えば、特許文献１及び２参照）。しかし、これら従来の混和剤には、これらを前記したような後添加混和剤として使用すると、コンクリートの流動性が高くなり過ぎたり、その割には流動保持性が低いという問題がある。混和剤の後添加によりコンクリートの流動性が高くなり過ぎると、コンクリートが材料分離を引き起こし、品質が低下する。 In order to improve the fluidity and fluid retention of concrete, various admixtures such as naphthalene-based, melamine-based, aminosulfonic acid-based or polycarboxylic acid-based materials are used at the time of preparation (for example, Patent Document 1 and 2). However, when these conventional admixtures are used as a post-addition admixture as described above, there is a problem that the fluidity of the concrete becomes too high or the fluidity retention is low. If the fluidity of the concrete becomes too high due to the post-addition of the admixture, the concrete causes material separation and the quality deteriorates.
本発明が解決しようとする課題は、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができるコンクリート用後添加混和剤を提供する処にある。 The problem to be solved by the present invention is that a post-added admixture for concrete that can maintain the fluidity of the concrete for a long time in a state immediately before the post-addition by post-adding to the prepared concrete that has not yet solidified It is in place to provide.
しかして本発明者らは、前記の課題を解決するべく研究した結果、コンクリート用後添加混和剤としては、分子中に特定の構成単位を有する共重合体の一つ又は二つ以上からなる特定のものが正しく好適であることを見出した。 Accordingly, as a result of studies conducted by the present inventors to solve the above-described problems, the post-additive admixture for concrete is specified as one or more of copolymers having specific structural units in the molecule. Was found to be correct and suitable.
すなわち本発明は、調製したまだ固まっていないコンクリートに後添加するコンクリート用後添加混和剤であって、下記の構成単位Ａと、下記の構成単位Ｂと、全構成単位の０〜２０質量％の範囲内の他の構成単位Ｃとから構成された共重合体の一つ又は二つ以上から成り、且つ全体の酢酸換算含有割合が０．１〜４．０質量％であるものから成ることを特徴とするコンクリート用後添加混和剤に係る。 That is, the present invention is a concrete post-additive admixture for post-adding to prepared concrete that has not yet solidified, comprising the following structural unit A, the following structural unit B, and 0 to 20% by mass of the total structural unit. It is composed of one or more copolymers composed of other structural units C in the range, and the total content in terms of acetic acid is 0.1 to 4.0% by mass. The post-additive admixture for concrete is characterized.
構成単位Ａ：下記の化１で示される単量体から選ばれる一つ又は二つ以上から形成された構成単位 Structural unit A: a structural unit formed from one or more selected from monomers represented by the following chemical formula 1
構成単位Ｂ：（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸及びそれらの塩から選ばれる一つ又は二つ以上から形成された構成単位 Structural unit B: a structural unit formed of one or more selected from (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid and salts thereof
化１において、
Ｒ１：炭素数２〜５のアルケニル基、炭素数３又は４の不飽和アシル基
Ｒ２：水素原子、炭素数１〜２２のアルキル基又は炭素数１〜２２の脂肪族アシル基
Ａ：炭素数２〜４のオキシアルキレン基で構成された平均付加モル数１〜３００個の（ポリ）オキシアルキレン基In chemical formula 1,
R 1 : an alkenyl group having 2 to 5 carbon atoms, an unsaturated acyl group having 3 or 4 carbon atoms R 2 : a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aliphatic acyl group having 1 to 22 carbon atoms A: carbon (Poly) oxyalkylene group having an average addition mole number of 1 to 300 composed of oxyalkylene groups of 2 to 4
本発明に係るコンクリート用後添加混和剤（以下、単に本発明の後添加混和剤という）は、調製したまだ固まっていないコンクリートに後添加するもので、前記の構成単位Ａと構成単位Ｂと全構成単位の０〜２０質量％の範囲内の他の構成単位Ｃとから構成された共重合体の一つ又は二つ以上から成るものである。 The post-additive admixture for concrete according to the present invention (hereinafter, simply referred to as the post-additive admixture of the present invention) is a post-addition to the prepared concrete that has not yet been solidified. It consists of one or two or more copolymers composed of other structural units C within the range of 0 to 20% by mass of the structural units.
構成単位Ａを形成することとなる化１で示される単量体において、化１中のＲ１としては、１）ビニル基、アリル基、メタリル基、３−ブテニル基、２−メチル−１−ブテニル基、３−メチル−１−ブテニル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基等の炭素数２〜５のアルケニル基、２）アクリロイル基、メタクリロイル基等の炭素数３〜４の不飽和アシル基が挙げられる。なかでも化１中のＲ１としては、アリル基、メタリル基、３−メチル−１−ブテニル基、アクリロイル基、メタクリロイル基が好ましい。In the monomer represented by Chemical Formula 1 that forms the structural unit A, R 1 in Chemical Formula 1 is 1) vinyl group, allyl group, methallyl group, 3-butenyl group, 2-methyl-1- C2-C5 alkenyl group such as butenyl group, 3-methyl-1-butenyl group, 2-methyl-3-butenyl group and 3-methyl-3-butenyl group, 2) carbon such as acryloyl group and methacryloyl group The unsaturated acyl group of number 3-4 is mentioned. Among them, R 1 in Chemical Formula 1 is preferably an allyl group, a methallyl group, a 3-methyl-1-butenyl group, an acryloyl group, or a methacryloyl group.
化１中のＲ２としては、１）水素原子、２）メチル基、エチル基、ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基、ヘンエイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、２−メチル−ペンチル基、２−エチル−ヘキシル基、２−プロピル−ヘプチル基、２−ブチル−オクチル基、２−ペンチル−ノニル基、２−ヘキシル−デシル基、２−ヘプチル−ウンデシル基、２−オクチル−ドデシル基、２−ノニル−トリデシル基、２−デシル−テトラデシル基、２−ウンデシル−ペンタデシル基、２−ドデシル−ヘキサデシル基等の炭素数１〜２２のアルキル基、３）ホルミル基、アセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、エイコセノイル基、オクタデセノイル基等の炭素数１〜２２の脂肪族アシル基が挙げられる。なかでも化１中のＲ２としては、水素原子、炭素数１〜４のアルキル基、炭素数１〜４の脂肪族アシル基が好ましい。As R 2 in Chemical Formula 1, 1) hydrogen atom, 2) methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, 2-methyl-pentyl group, 2- Ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2-pentyl-nonyl group, 2-hexyl-decyl group, 2-heptyl-undecyl group, 2-octyl-dodecyl group, 2-nonyl -Tridecyl group, 2-decyl-tetradecyl group, 2-undecyl-pentadecyl Groups, alkyl groups having 1 to 22 carbon atoms such as 2-dodecyl-hexadecyl group, 3) formyl group, acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecane C1-C22 aliphatic acyl groups, such as a noyl group, an octadecanoyl group, a hexadecenoyl group, an eicosenoyl group, an octadecenoyl group, are mentioned. Among these, R 2 in Chemical Formula 1 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aliphatic acyl group having 1 to 4 carbon atoms.
化１中のＡとしては、１）炭素数２〜４のオキシアルキレン基、２）合計２〜３００個の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基が挙げられる。なかでも化１中のＡとしては、合計１〜１６０個のオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基が好ましい。 Examples of A in Chemical Formula 1 include 1) an oxyalkylene group having 2 to 4 carbon atoms, and 2) a polyoxyalkylene group composed of a total of 2 to 300 oxyalkylene units having 2 to 4 carbon atoms. Among these, as A in Chemical Formula 1, a (poly) oxyalkylene group composed of a total of 1 to 160 oxyethylene units and / or oxypropylene units is preferable.
以上説明した化１で示される単量体の具体例としては、α−アリル−ω−アセチル−（ポリ）オキシエチレン、α−アリル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタリル−ω−メトキシ−（ポリ）オキシエチレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、−メタリル−ω−アセチル−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ブトキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−（３−メチル−３−ブテニル）−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、α−アクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン等が挙げられる。 Specific examples of the monomer represented by Chemical Formula 1 described above include α-allyl-ω-acetyl- (poly) oxyethylene, α-allyl-ω-acetyl- (poly) oxyethylene (poly) oxypropylene, α-allyl-ω-hydroxy- (poly) oxyethylene, α-allyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methallyl-ω-hydroxy- (poly) oxyethylene, α-methallyl -Ω-methoxy- (poly) oxyethylene, α-methallyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, -methallyl-ω-acetyl- (poly) oxyethylene, α- (3-methyl- 3-butenyl) -ω-hydroxy- (poly) oxyethylene, α- (3-methyl-3-butenyl) -ω-butoxy- (poly) oxyethylene , Α- (3-methyl-3-butenyl) -ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α- (3-methyl-3-butenyl) -ω-acetyl- (poly) oxyethylene ( Poly) oxypropylene, hydroxyethyl acrylate, hydroxypropyl acrylate, α-acryloyl-ω-hydroxy- (poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene, α-acryloyl-ω-butoxy- ( Poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene, α-methacryloyl-ω-methoxy- (poly) oxy Ethylene, α-methacryloyl-ω-butoxy- (poly) oxyethylene Len, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-acetyl- (poly ) Oxyethylene (poly) oxypropylene and the like.
化１で示される単量体としては、以上例示した単量体の一つ又は二つ以上を用いることができるが、なかでもヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを含むものを用いるのが好ましく、化１で示される単量体中にヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを３〜３０質量％含むものがより好ましい。 As the monomer represented by Chemical Formula 1, one or more of the monomers exemplified above can be used, and among them, hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate are included. It is preferable to use those, and those containing 3 to 30% by mass of hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate in the monomer represented by Chemical Formula 1 are more preferable.
構成単位Ｂを形成することとなる単量体としては、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸及びそれらの塩が挙げられる。なかでも構成単位Ｂを形成することとなる単量体としては、（メタ）アクリル酸、マレイン酸、（メタ）アクリル酸塩、マレイン酸塩が好ましい。 Examples of the monomer that forms the structural unit B include (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, and salts thereof. Among these, as the monomer that forms the structural unit B, (meth) acrylic acid, maleic acid, (meth) acrylate, and maleate are preferable.
構成単位Ｂを形成することとなる単量体の塩としては、特に制限するものではないが、これには例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。 The salt of the monomer that forms the structural unit B is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, and alkaline earth salts such as calcium salt and magnesium salt. Examples thereof include metal salts, ammonium salts, amine salts such as diethanolamine salts and triethanolamine salts.
他の構成単位Ｃを形成することとなる単量体としては、（メタ）アリルスルホン酸、（メタ）アリルスルホン酸塩、アクリルアミド、メタクリルアミド、アクリロニトリル、（メタ）アクリル酸エステル等が挙げられる。 Examples of the monomer that forms the other structural unit C include (meth) allyl sulfonic acid, (meth) allyl sulfonate, acrylamide, methacrylamide, acrylonitrile, (meth) acrylic acid ester, and the like.
本発明の後添加混和剤として用いる共重合体は、構成単位Ａと構成単位Ｂを必須の構成単位とし、他の構成単位Ｃを任意の構成単位とするものである。かかる共重合体における構成単位Ａの含有割合は全構成単位中に８０〜９９．５質量％とするのが好ましく、また構成単位Ｂの含有割合は全構成単位中に０．５〜２０質量％とするのが好ましい。他の構成単位Ｃの含有割合は全構成単位中に０〜２０質量％とするが、全構成単位中に０〜１０質量％とするのが好ましい。 The copolymer used as the post-additive admixture of the present invention has the structural unit A and the structural unit B as essential structural units, and the other structural unit C as an arbitrary structural unit. The content of the structural unit A in the copolymer is preferably 80 to 99.5% by mass in all the structural units, and the content of the structural unit B is 0.5 to 20% by mass in all the structural units. Is preferable. Although the content rate of the other structural unit C shall be 0-20 mass% in all the structural units, it is preferable to set it as 0-10 mass% in all the structural units.
本発明の後添加混和剤は以上説明した共重合体の一つ又は二つ以上から成るものであるが、全体の酢酸換算含有割合が０．１〜４．０質量％、好ましくは０．１〜３．０質量％の共重合体から成るものである。本発明において、酢酸換算含有割合は、本発明の後添加混和剤を構成する共重合体に含まれるカルボキシル基及びその塩を電位差滴定して酢酸に換算したときの質量％であり、具体的には、共重合体の４０質量％水溶液をイオン交換水で２０倍に希釈した２質量％水溶液に塩酸水溶液を加えてｐＨ２としたものを電位差滴定装置に供し、これを濃度０．１モル／Ｌの水酸化カリウム水溶液で滴定したときの、第１当量点と第２当量点との間に消費された水酸化カリウムと同モルの酢酸の質量を求め、求めた酢酸の質量の元の共重合体の質量に対する割合を算出した値（質量％）である。本発明において、全体の酢酸換算含有割合は、本発明の後添加混和剤が一つの共重合体から成るものである場合には、該一つの共重合体の酢酸換算含有割合であり、また本発明の後添加混和剤が二つ以上の共重合体から成るものである場合には、該二つ以上の共重合体における各共重合体の酢酸換算含有割合の加重平均値である。 The post-additive admixture of the present invention comprises one or two or more of the above-described copolymers, but the total acetic acid content is 0.1 to 4.0% by mass, preferably 0.1 It is composed of ˜3.0 mass% copolymer. In the present invention, the acetic acid equivalent content ratio is mass% when converted into acetic acid by potentiometric titration of the carboxyl group and its salt contained in the copolymer constituting the post-additive admixture of the present invention, specifically Prepared by adding a hydrochloric acid aqueous solution to a 2% by weight aqueous solution obtained by diluting a 40% by weight aqueous solution of the copolymer 20 times with ion-exchanged water and adjusting the pH to 2 and supplying the resulting solution to a potentiometric titrator. The amount of acetic acid in the same mole as potassium hydroxide consumed between the first equivalent point and the second equivalent point when titrated with an aqueous potassium hydroxide solution was determined. It is the value (mass%) which calculated the ratio with respect to the mass of coalescence. In the present invention, the total acetic acid equivalent content ratio is the acetic acid equivalent content ratio of the one copolymer when the post-additive admixture of the present invention is composed of one copolymer. When the post-additive admixture of the invention is composed of two or more copolymers, it is a weighted average value of acetic acid equivalent content of each copolymer in the two or more copolymers.
本発明の後添加混和剤に用いる共重合体それ自体は、公知の方法で製造することができる。これには、溶媒に水を用いたラジカル重合、溶媒に有機溶媒を用いたラジカル重合、無溶媒のラジカル重合がある。ラジカル重合に用いるラジカル重合開始剤は、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過酸化物やアゾビスイソブチロニトリルのように、重合反応温度下において分解し、ラジカル発生するものであればその種類は特に制限されない。得られる共重合体の質量平均分子量を所望の範囲とするため、連鎖移動剤を使用することもできる。 The copolymer itself used for the post-addition admixture of the present invention can be produced by a known method. This includes radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and solvent-free radical polymerization. The radical polymerization initiator used for radical polymerization decomposes at the polymerization reaction temperature, such as peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, and azobisisobutyronitrile, generating radicals. If it does, the kind in particular will not be restrict | limited. In order to make the mass average molecular weight of the copolymer obtained into a desired range, a chain transfer agent can also be used.
本発明の後添加混和剤の使用に際しては、得られた共重合体を単独で使用することもできるし、異なる共重合体の二つ以上を混合して使用することもできる。共重合体の二つ以上を混合して使用する場合には、少なくとも一つの共重合体がヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを含む化１で示される単量体から形成された構成単位Ａを有することが好ましい。また本発明の後添加混和剤の使用に際しては、本発明の効果を損なわない範囲内で、凝結遅延剤、凝結促進剤、防錆剤、ＡＥ剤、消泡剤等を併用することもできる。 In using the post-additive admixture of the present invention, the obtained copolymer can be used alone, or two or more different copolymers can be mixed and used. When two or more copolymers are used as a mixture, at least one copolymer is selected from monomers represented by Chemical Formula 1 containing hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate. It is preferable to have the structural unit A formed. Moreover, when using the post-added admixture of the present invention, a setting retarder, a setting accelerator, a rust inhibitor, an AE agent, an antifoaming agent and the like can be used in combination as long as the effects of the present invention are not impaired.
本発明の後添加混和剤は、調製したまだ固まっていないコンクリートに後添加するものである。かかるコンクリートの構成材料に特に制限はなく、例えば結合材としては、１）普通ポルトランドセメント、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、低熱ポルトランドセメント等の各種ポルトランドセメント、２）高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメント、３）アルミナセメント等が挙げられる。また水／結合材比も特に制限はないが、水／結合材比は３０〜７０％のものが好ましく、３５〜６５％のものがより好ましい。更にかかるコンクリートの調製に使用する分散剤の種類にも特に制限はないが、分散剤としてはオキシカルボン酸やその塩、ポリカルボン酸系、リグニンスルホン酸系のものから選ばれる一つ又は二つ以上が好ましい。 The post-added admixture of the present invention is post-added to prepared concrete that has not yet set. There are no particular restrictions on the constituent material of such concrete. For example, as a binder, 1) various portland cements such as ordinary portland cement, early strong portland cement, medium heat portland cement, low heat portland cement, etc., 2) blast furnace cement, fly ash cement And various mixed cements such as silica fume cement, and 3) alumina cement. The water / binder ratio is not particularly limited, but the water / binder ratio is preferably 30 to 70%, more preferably 35 to 65%. Further, the type of the dispersant used for the preparation of such concrete is not particularly limited, but the dispersant is one or two selected from oxycarboxylic acid and salts thereof, polycarboxylic acid type, lignin sulfonic acid type. The above is preferable.
本発明の後添加混和剤の使用量は、調製したまだ固まっていないコンクリート中の結合材１００質量部に対し、固形分換算で、通常は０．０１〜１．０質量部、好ましくは０．０１〜０．５質量部、より好ましくは０．０２〜０．５質量部とする。 The amount of the post-additive admixture used in the present invention is usually 0.01 to 1.0 parts by mass, preferably 0.00, in terms of solid content with respect to 100 parts by mass of the binder in the prepared concrete that has not yet solidified. 01 to 0.5 parts by mass, more preferably 0.02 to 0.5 parts by mass.
本発明によると、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、増大させることなく、後添加直前の状態に長時間にわたって保持することができる。 According to the present invention, by post-adding to the prepared concrete which has not yet been solidified, the fluidity of the concrete can be maintained for a long time without increasing the concrete flow.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（共重合体の合成）
・共重合体（Ｓ−１）の合成
イオン交換水７６．６ｇ及びα−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝１１５、ｎはオキシエチレン単位の数、以下同じ）オキシエチレン１５６．４ｇを、温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器（以下、同様のものを使用した）に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。次に１％過酸化水素水８．８ｇを３時間かけて滴下し、またそれと同時に、イオン交換水３９．１ｇにヒドロキシエチルアクリレート１５．６ｇとアクリル酸３．９ｇとアクリル酸メチル１９．５ｇを均一に溶解させた水溶液を３時間かけて滴下し、更にそれと同時に、イオン交換水７．０ｇにＬ−アスコルビン酸０．８ｇとチオグリコール酸１．０ｇを溶解させた水溶液を４時間かけて滴下した。その後６５℃で２時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−１）の４０％水溶液を得た。Test Category 1 (Synthesis of copolymer)
Synthesis of copolymer (S-1) 76.6 g of ion-exchanged water and α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 115, n is the number of oxyethylene units, and so on. ) Charge 156.4 g of oxyethylene into a reaction vessel (hereinafter, the same one is used) equipped with a thermometer, stirrer, dropping funnel and nitrogen introducing tube, dissolve uniformly with stirring, and then add nitrogen to the atmosphere. The temperature of the reaction system was set to 65 ° C. with a warm water bath. Next, 8.8 g of 1% hydrogen peroxide solution was added dropwise over 3 hours. At the same time, 15.6 g of hydroxyethyl acrylate, 3.9 g of acrylic acid and 19.5 g of methyl acrylate were added to 39.1 g of ion-exchanged water. A uniformly dissolved aqueous solution was added dropwise over 3 hours, and at the same time, an aqueous solution prepared by dissolving 0.8 g of L-ascorbic acid and 1.0 g of thioglycolic acid in 7.0 g of ion-exchanged water was added dropwise over 4 hours. did. Thereafter, the polymerization reaction was completed by maintaining at 65 ° C. for 2 hours. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution is added to adjust the reaction system to pH 6, and the concentration is adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-1). It was.
・共重合体（Ｓ−２）の合成
イオン交換水７８．０ｇを反応容器に仕込み、攪拌しながら雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。イオン交換水１４１．７ｇ、α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレン１４７．８ｇ、ヒドロキシエチルアクリレート４５．３ｇ、メタクリル酸３．９ｇ及びメルカプトエタノール１．４ｇを均一に溶解させた水溶液を２時間かけて滴下すると共に、１０％過硫酸アンモニウム２８．６ｇを３時間かけて滴下した。その後６５℃で１時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体１（Ｓ−２）の４０％水溶液を得た。-Synthesis | combination of copolymer (S-2) 78.0g of ion-exchange water was prepared to reaction container, atmosphere was substituted with nitrogen, stirring, and the temperature of the reaction system was 65 degreeC with the hot water bath. 141.7 g of ion-exchanged water, 147.8 g of α-methacryloyl-ω-methoxy-poly (n = 9) oxyethylene, 45.3 g of hydroxyethyl acrylate, 3.9 g of methacrylic acid and 1.4 g of mercaptoethanol are uniformly dissolved. The aqueous solution was added dropwise over 2 hours, and 28.6 g of 10% ammonium persulfate was added dropwise over 3 hours. Thereafter, the polymerization reaction was completed by maintaining at 65 ° C. for 1 hour. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution is added to adjust the reaction system to pH 6, the concentration is adjusted to 40% with ion-exchanged water, and a 40% aqueous solution of copolymer 1 (S-2) is prepared. Obtained.
・共重合体（Ｓ−３）の合成
イオン交換水２８．１ｇ、α−（メタリル）−ω−ヒドロキシ−ポリ（ｎ＝５３）オキシエチレン１５６．３ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃とした。次に５％過酸化水素水溶液６．９ｇを３時間かけて滴下し、またそれと同時に、イオン交換水１５６．３ｇにヒドロキシエチルアクリレート３７．９ｇとアクリル酸１．２ｇを均一に溶解させた水溶液を３時間かけて滴下し、更にそれと同時に、イオン交換水５．５ｇにＬ−アスコルビン酸０．８ｇと３−メルカプトプロピオン酸０．６ｇを溶解させた水溶液を３時間かけて滴下した。その後７０℃で１時間維持し、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−３）の４０％水溶液で得た。-Synthesis of copolymer (S-3) Charged 28.1 g of ion-exchanged water and 156.3 g of α- (methallyl) -ω-hydroxy-poly (n = 53) oxyethylene into a reaction vessel and stirred uniformly. After dissolution, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70 ° C. in a warm water bath. Next, 6.9 g of a 5% hydrogen peroxide aqueous solution was dropped over 3 hours, and at the same time, an aqueous solution in which 37.9 g of hydroxyethyl acrylate and 1.2 g of acrylic acid were uniformly dissolved in 156.3 g of ion-exchanged water. The solution was added dropwise over 3 hours, and at the same time, an aqueous solution prepared by dissolving 0.8 g of L-ascorbic acid and 0.6 g of 3-mercaptopropionic acid in 5.5 g of ion-exchanged water was added dropwise over 3 hours. Thereafter, the polymerization reaction was completed by maintaining at 70 ° C. for 1 hour. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-3).
・共重合体（Ｓ−４）の合成
イオン交換水２１４．０ｇ、α−メタクリロイル−ω−ヒドロキシ−ポリ（ｎ＝２１）オキシエチレンポリ（ｍ＝２、ｍはオキシプロピレン単位の数、以下同じ）オキシプロピレン１４７．１ｇ、メタクリル酸３４．４ｇ、アクリル酸ブチル９．６ｇ及び３−メルカプトプロピオン酸１．５ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて６０℃に保ち、１０％過硫酸ナトリウム水溶液２７．７ｇを４時間かけて投入した。更に６０℃で２時間保持して、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−４）の４０％水性液を得た。-Synthesis of copolymer (S-4) 214.0 g of ion-exchanged water, α-methacryloyl-ω-hydroxy-poly (n = 21) oxyethylene poly (m = 2, m is the number of oxypropylene units, and so on. ) 147.1 g of oxypropylene, 34.4 g of methacrylic acid, 9.6 g of butyl acrylate and 1.5 g of 3-mercaptopropionic acid were charged in a reaction vessel and dissolved uniformly with stirring, and then the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60 ° C. in a warm water bath, and 27.7 g of a 10% aqueous sodium persulfate solution was added over 4 hours. Further, the polymerization reaction was completed by maintaining at 60 ° C. for 2 hours. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-4).
・共重合体（Ｓ−５）の合成
イオン交換水２１５．４ｇ、α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレン１６６．９ｇ、メタクリル酸２４．９ｇ及び３−メルカプトプロピオン酸１．９ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて６０℃に保ち、１０％過硫酸ナトリウム水溶液２２．３ｇを投入した。６０℃で３時間保持した後、１０％過硫酸ナトリウム水溶液５．６ｇを加えた。更に６０℃で２時間保持して、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−５）の４０％水性液を得た。Synthesis of copolymer (S-5) 215.4 g of ion exchange water, α-methacryloyl-ω-methoxy-poly (n = 9) oxyethylene 166.9 g, methacrylic acid 24.9 g and 3-mercaptopropionic acid 1 .9 g was charged into a reaction vessel and dissolved uniformly with stirring, and the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60 ° C. in a warm water bath, and 22.3 g of a 10% aqueous sodium persulfate solution was added. After maintaining at 60 ° C. for 3 hours, 5.6 g of a 10% aqueous sodium persulfate solution was added. Further, the polymerization reaction was completed by maintaining at 60 ° C. for 2 hours. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-5).
・共重合体（Ｓ−６）の合成
無水マレイン酸１４７ｇ及びα−アリル−ω−メトキシ−ポリ（ｎ＝５０）オキシエチレン１５２７ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて８０℃に保ち、アゾビスイソブチロニトリル１０．０ｇを投入して、ラジカル共重合反応を開始した。１時間後、更にアゾビスイソブチロニトリル５．０ｇを投入し、その１時間後、更にアゾビスイソブチロニトリル５．０ｇを投入して、５時間ラジカル共重合反応を行なった後、反応系にイオン交換水３００ｇを加えてラジカル共重合反応を停止した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ５に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−６）の４０％水溶液を得た。Synthesis of copolymer (S-6) 147 g of maleic anhydride and 1527 g of α-allyl-ω-methoxy-poly (n = 50) oxyethylene were charged in a reaction vessel and dissolved uniformly with stirring, and then the atmosphere was changed. Replaced with nitrogen. The temperature of the reaction system was kept at 80 ° C. in a warm water bath, and 10.0 g of azobisisobutyronitrile was added to start radical copolymerization reaction. After 1 hour, 5.0 g of azobisisobutyronitrile was added, and after 1 hour, 5.0 g of azobisisobutyronitrile was further added, and a radical copolymerization reaction was performed for 5 hours. 300 g of ion exchange water was added to the system to stop the radical copolymerization reaction. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 5, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-6).
・共重合体（Ｓ−７）の合成
特開２００７―１１９３３７号公報の段落「００６７」に記載された製造例１の方法で製造を行い、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ―７）の４０％水溶液を得た。-Synthesis of copolymer (S-7) The copolymer (S-7) was prepared by the method of Production Example 1 described in paragraph "0067" of JP-A No. 2007-119337, and the concentration was adjusted to 40% with ion-exchanged water. A 40% aqueous solution of copolymer (S-7) was obtained.
・共重合体（Ｓ−８）の合成
特開２０１１―０２６１６７号公報の段落「００２５」に記載された方法で製造を行い、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ―８）の４０％水溶液を得た。-Synthesis of copolymer (S-8) Manufactured by the method described in paragraph "0025" of JP2011-026167A, adjusted to a concentration of 40% with ion-exchanged water, and copolymer A 40% aqueous solution of (S-8) was obtained.
製造した各共重合体の質量平均分子量をゲルパーミエーションクロマトグラフィーにて測定すると共に、酢酸換算含有割合を前記の方法にて測定した。各共重合体の内容及び測定結果を表１にまとめて示した。 While measuring the mass mean molecular weight of each manufactured copolymer by gel permeation chromatography, the acetic acid conversion content rate was measured by the said method. The contents and measurement results of each copolymer are summarized in Table 1.
表１において、
Ａ−１：α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝１１５）オキシエチレンから形成された構成単位
Ａ−２：α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレンから形成された構成単位
Ａ−３：α−メタリル−ω−ヒドロキシ−ポリ（ｎ＝５３）オキシエチレンから形成された構成単位
Ａ−４：α−メタクリロイル−ω−ヒドロキシ−ポリ（ｎ＝２１）オキシエチレンポリ（ｍ＝２、ｍはオキシプロピレン単位の数、以下同じ）オキシプロピレンから形成された構成単位
Ａ−５：α−アリル−ω−メトキシ−ポリ（ｎ＝５０）オキシエチレンから形成された構成単位
Ａ−６：ヒドロキシエチルアクリレートから形成された構成単位
Ａ−７：α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝５０）オキシエチレンから形成された構成単位
Ａ−８：α−アリル−ω−メトキシ−ポリ（ｎ＝３３）オキシエチレンから形成された構成単位
Ｂ−１：アクリル酸から形成された構成単位
Ｂ−２：メタクリル酸から形成された構成単位
Ｂ−３：マレイン酸から形成された構成単位
Ｃ−１：アクリル酸メチルから形成された構成単位
Ｃ−２：アクリル酸ブチルから形成された構成単位In Table 1,
A-1: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 115) structural unit formed from oxyethylene A-2: α-methacryloyl-ω-methoxy-poly (n = 9) Structural unit formed from oxyethylene A-3: α-methallyl-ω-hydroxy-poly (n = 53) Structural unit formed from oxyethylene A-4: α-methacryloyl-ω-hydroxy-poly ( n = 21) Oxyethylene poly (m = 2, m is the number of oxypropylene units, the same shall apply hereinafter) A structural unit formed from oxypropylene A-5: α-allyl-ω-methoxy-poly (n = 50) oxy Structural unit formed from ethylene A-6: Structural unit formed from hydroxyethyl acrylate A-7: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n 50) Structural unit formed from oxyethylene A-8: Structural unit formed from α-allyl-ω-methoxy-poly (n = 33) oxyethylene B-1: Structural unit formed from acrylic acid B- 2: Structural unit formed from methacrylic acid
B-3: Structural unit formed from maleic acid
C-1: Structural unit formed from methyl acrylate C-2: Structural unit formed from butyl acrylate
試験区分２（後添加混和剤の調製）
・実施例１（後添加混和剤（Ｐ−１）の調製）
前記の共重合体（Ｓ−３）をそのまま後添加混和剤（Ｐ−１）とした。したがって全体の酢酸換算含有割合は０．７％である。使用に際しては、前記の共重合体（Ｓ−３）の水溶液を更にイオン交換水で希釈して２０％水溶液とした。Test Category 2 (Preparation of post-additive admixture)
Example 1 (Preparation of post-added admixture (P-1))
The copolymer (S-3) was directly used as a post-additive admixture (P-1). Therefore, the total acetic acid content is 0.7%. In use, the aqueous solution of the copolymer (S-3) was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例２（後添加混和剤（Ｐ−２）の調製）
前記の共重合体（Ｓ−１）をそのまま後添加混和剤（Ｐ−２）とした。したがって全体の酢酸換算含有割合は１．７％である。使用に際しては、前記の共重合体（Ｓ−１）の水溶液を更にイオン交換水で希釈して２０％水溶液とした。Example 2 (Preparation of post-added admixture (P-2))
The copolymer (S-1) was used as the post-added admixture (P-2) as it was. Therefore, the total acetic acid equivalent content is 1.7%. In use, the aqueous solution of the copolymer (S-1) was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例３（後添加混和剤（Ｐ−３）の調製）
前記の共重合体（Ｓ−２）が９０部及び前記の共重合体（Ｓ−４）が１０部の割合となるように均一混合したものを後添加混和剤（Ｐ−３）とした。したがって全体の酢酸換算含有割合は２．５％である。使用に際しては、前記の双方の水溶液の混合液を更にイオン交換水で希釈して２０％水溶液とした。Example 3 (Preparation of post-added admixture (P-3))
What was uniformly mixed so that the copolymer (S-2) was 90 parts and the copolymer (S-4) was 10 parts was used as a post-added admixture (P-3). Therefore, the total acetic acid equivalent content is 2.5%. In use, the mixture of both aqueous solutions was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例４〜６（後添加混和剤（Ｐ−４）〜（Ｐ−６）の調製）
実施例３の後添加混和剤（Ｐ−３）の場合と同様にして、表２に記載の内容で、後添加混和剤（Ｐ−４）〜（Ｐ−６）を調製した。Examples 4 to 6 (Preparation of post-added admixtures (P-4) to (P-6))
In the same manner as in the case of the post-additive admixture (P-3) of Example 3, post-addition admixtures (P-4) to (P-6) were prepared with the contents shown in Table 2.
・比較例１〜６（後添加混和剤（Ｒ−１）〜（Ｒ−６）、（Ｒ−９）及び（Ｒ−１０）の調製）
実施例１、２又は３の後添加混和剤（Ｐ−１）、（Ｐ−２）又は（Ｐ−３）の場合と同様にして、表２に記載の内容で、後添加混和剤（Ｒ−１）〜（Ｒ−６）、（Ｒ−９）、（Ｒ―１０）を調製した。Comparative Examples 1 to 6 (Preparation of post-added admixtures (R-1) to (R-6), (R-9) and (R-10))
In the same manner as in the case of the post-additive admixture (P-1), (P-2) or (P-3) of Examples 1, 2, or 3, the post-additive admixture (R -1) to (R-6), (R-9) and (R-10) were prepared.
・比較例７（後添加混和剤（Ｒ−７）の調製）
凝結遅延剤として市販されているポリヒドロキシカルボン酸複合体（竹本油脂社製の凝結遅延剤Ｔ−２１）をそのまま後添加混和剤（Ｒ−７）とした。使用に際してはイオン交換水で水希釈して２０％水溶液とした。Comparative Example 7 (Preparation of post-added admixture (R-7))
A polyhydroxycarboxylic acid complex (setting retarder T-21 manufactured by Takemoto Yushi Co., Ltd.) commercially available as a setting retarder was used as the post-added admixture (R-7). At the time of use, it was diluted with ion-exchanged water to make a 20% aqueous solution.
・比較例８（後添加混和剤（Ｒ−８）の調製）
流動化剤として市販されているアルキルアリルスルホン酸塩高縮合物（竹本油脂社製の流動化剤ハイフルード）をそのまま後添加混和剤（Ｒ−８）とした。使用に際してはイオン交換水で水希釈して２０％水溶液とした。Comparative Example 8 (Preparation of post-added admixture (R-8))
Alkyl allyl sulfonate high condensate commercially available as a fluidizing agent (Fluidizing agent fluid made by Takemoto Yushi Co., Ltd.) was used as it was as a post-additive admixture (R-8). At the time of use, it was diluted with ion-exchanged water to make a 20% aqueous solution.
以上で調製した各例の後添加混和剤（Ｐ−１）〜（Ｐ−６）及び（Ｒ−１）〜（Ｒ−８）の内容を表２にまとめて示した。 The contents of the post-added admixtures (P-1) to (P-6) and (R-1) to (R-8) of each example prepared above are summarized in Table 2.
表２において、
比較例７及び８：構成単位Ａ及びＢを有する構造のものではない。 In Table 2,
Comparative Examples 7 and 8: The structure does not have the structural units A and B.
試験区分３（コンクリートの調製、後添加混和剤の後添加及び評価）
・コンクリートの調製
５５Ｌの強制二軸ミキサーに、表３に記載の内容で、普通ポルトランドセメント（太平洋セメント社製、比重＝３．１６）、細骨材（大井川水系砂、比重＝２．５８）及び粗骨材（岡崎産砕石、比重＝２．６８）を順次投入して５秒間空練りした後、目標スランプフローが１５±２．５ｃｍ及び空気量が４．５±０．５％の範囲となるよう、ＡＥ減水剤（竹本油脂社製の商品名チューポールＥＸ２０）をセメントに対し１％、ＡＥ剤（竹本油脂社製の商品名ＡＥ−３００）をセメントに対し０．００５％及び消泡剤（竹本油脂社製の商品名ＡＦＫ−２）をセメントに対し０．００１％となるよう練混ぜ水と共に投入し、９０秒間練混ぜて、コンクリートを調製した。このコンクリートを用い、温度２０±３℃、湿度６０％の雰囲気下にて、以下のように試験を行なった。結果を表４及び表５にまとめて示した。Test category 3 (preparation of concrete, post-addition of post-additives and evaluation)
・ Preparation of concrete In 55L forced biaxial mixer, with the contents shown in Table 3, ordinary Portland cement (manufactured by Taiheiyo Cement, specific gravity = 3.16), fine aggregate (Oikawa water sand, specific gravity = 2.58) And after adding coarse aggregate (Okazaki crushed stone, specific gravity = 2.68) sequentially and kneading for 5 seconds, the target slump flow is 15 ± 2.5cm and the air volume is in the range of 4.5 ± 0.5% 1% of AE water-reducing agent (trade name Tupole EX20 manufactured by Takemoto Yushi Co., Ltd.) for cement, 0.005% for AE agent (trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.) A foaming agent (trade name AFK-2 manufactured by Takemoto Yushi Co., Ltd.) was added together with mixing water so as to be 0.001% with respect to cement, and was mixed for 90 seconds to prepare concrete. Using this concrete, the test was performed as follows in an atmosphere of a temperature of 20 ± 3 ° C. and a humidity of 60%. The results are summarized in Table 4 and Table 5.
練混ぜ直後から２０分静置の時点で、コンクリートに後添加混和剤（Ｐ−１）〜（Ｐ−６）及び（Ｒ−１）〜（Ｒ−１０）を添加し（但し、試験例１０は未添加のブランク）、３０秒間練混ぜ、静置した。練混ぜ直後から３０分間隔で、静置したコンクリートのスランプを測定し、また２４時間静置後の硬化体のブリーディング率及び圧縮強度を次のように測定した。 At the time of standing for 20 minutes immediately after kneading, post-additives (P-1) to (P-6) and (R-1) to (R-10) were added to the concrete (however, Test Example 10) Was blank with no addition), mixed for 30 seconds and allowed to stand. The slump of the concrete that was allowed to stand was measured at intervals of 30 minutes immediately after mixing, and the bleeding rate and compressive strength of the cured product after being allowed to stand for 24 hours were measured as follows.
・スランプ：ＪＩＳ−Ａ１１５０に準拠して測定した。
・ブリーディング：ＪＩＳ−Ａ１１２３に準拠して測定した。
・圧縮強度：ＪＩＳ−Ａ１１０８に準拠し、供試体寸法を直径１００ｍｍ×長さ２００ｍｍとし、材齢２４時間で測定した。-Slump: Measured according to JIS-A1150.
-Bleeding: Measured according to JIS-A1123.
-Compressive strength: Based on JIS-A1108, the specimen size was 100 mm in diameter x 200 mm in length, and measured at a material age of 24 hours.
表４において、
添加量：セメントに対する後添加混和剤の添加量（％）
＊１：コンクリートの練混ぜ直後から２０分、５０分、８０分経過の各時点で後添加混和剤を０．１％ずつ後添加し、合計０．３％添加した。
＊２：コンクリートの練混ぜ直後から１０分経過の時点で後添加混和剤を０．３％後添加した。
＊３：後添加混和剤の後添加を行わなかった。In Table 4,
Addition amount: Addition amount of post-additive admixture to cement (%)
* 1: After each of 20 minutes, 50 minutes, and 80 minutes after the concrete was mixed, the post-added admixture was added by 0.1%, and a total of 0.3% was added.
* 2: After 10 minutes from immediately after mixing the concrete, the post-added admixture was added after 0.3%.
* 3: After-addition admixture was not added afterwards.
表５において、
＊４：硬化体が圧縮強度を測定できる強度に到達していなかった。In Table 5,
* 4: The cured product did not reach the strength at which the compressive strength could be measured.
図１は本発明の後添加混和剤等を後添加したコンクリートのスランプの変化を例示するグラフである。横軸に後添加混和剤等を加えた直後からの時間（分）を目盛り、また縦軸にスランプ（ｃｍ）を目盛っている。図１中、１は試験例１についてのスランプの変化を示す折れ線、１０は試験例１０についてのスランプの変化を示す折れ線（但し、試験例１０は後添加混和剤を未添加）、１５は試験例１５についてのスランプの変化を示す折れ線、１９は試験例１９についてのスランプの変化を示す折れ線である。 FIG. 1 is a graph illustrating the change in the slump of concrete to which the post-added admixture or the like of the present invention is post-added. The horizontal axis indicates the time (minutes) immediately after the addition of the post-added admixture and the like, and the vertical axis indicates the slump (cm). In FIG. 1, 1 is a polygonal line showing the change in slump for Test Example 1, 10 is a polygonal line showing the change in slump for Test Example 10 (however, Test Example 10 has no post-added admixture added), and 15 is the test. A polygonal line indicating the change in the slump for the example 15 and 19 is a polygonal line indicating the change in the slump for the test example 19.
表１〜表３に対応する表４及び表５の結果、更には図１の結果からも明らかなように、本発明の後添加混和剤によると、調製したまだ固まっていないコンクリートに後添加することによって、得られる硬化体のブリーディング率や圧縮強度に悪影響を及ぼすことなく、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができる。 As is apparent from the results of Tables 4 and 5 corresponding to Tables 1 to 3 and also from the results of FIG. 1, according to the post-additive of the present invention, the post-addition is performed on the prepared concrete that has not yet solidified. Thus, the fluidity of the concrete can be maintained for a long time in the state immediately before post-addition without adversely affecting the bleeding rate and compressive strength of the obtained cured product.
１ 試験例１についてのスランプの変化を示す折れ線
１０ 試験例１０についてのスランプの変化を示す折れ線
１５ 試験例１５についてのスランプの変化を示す折れ線
１９ 試験例１９についてのスランプの変化を示す折れ線DESCRIPTION OF SYMBOLS 1 Broken line which shows the change of slump about Test Example 1 10 Broken line which shows the change of slump about Test Example 10 15 Broken line which shows the change of slump about Test Example 15 19 Broken line which shows the change of slump about Test Example 19
本発明はコンクリート用後添加混和剤に関する。各種材料を練り混ぜてコンクリートを調製し、調製したコンクリートを実際の使用場所まで運搬して、運搬したコンクリートを使用する場合、例えば運搬に長時間を要し、調製したコンクリートの流動性が低下して、使用し難くなることがある。このような場合、調製したまだ固まっていないコンクリートに混和剤を後添加して、コンクリートの流動性を保持することが行なわれる。本発明は、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができる後添加混和剤に関する。 The present invention relates to a post-additive admixture for concrete. When mixing concrete materials to prepare concrete, transporting the prepared concrete to the actual place of use and using the transported concrete, for example, it takes a long time to transport, and the fluidity of the prepared concrete decreases. May be difficult to use. In such a case, an admixture is post-added to the prepared concrete that has not yet solidified to maintain the fluidity of the concrete. The present invention relates to a post-added admixture that can maintain the fluidity of concrete over a long period of time in a state immediately before post-addition by post-adding to the prepared concrete that has not yet solidified.
コンクリートの流動性や流動保持性を向上するため、その調製時に、ナフタレン系、メラミン系、アミノスルホン酸系又はポリカルボン酸系等の各種の混和剤が使用されている（例えば、特許文献１及び２参照）。しかし、これら従来の混和剤には、これらを前記したような後添加混和剤として使用すると、コンクリートの流動性が高くなり過ぎたり、その割には流動保持性が低いという問題がある。混和剤の後添加によりコンクリートの流動性が高くなり過ぎると、コンクリートが材料分離を引き起こし、品質が低下する。 In order to improve the fluidity and fluid retention of concrete, various admixtures such as naphthalene-based, melamine-based, aminosulfonic acid-based or polycarboxylic acid-based materials are used at the time of preparation (for example, Patent Document 1 and 2). However, when these conventional admixtures are used as a post-addition admixture as described above, there is a problem that the fluidity of the concrete becomes too high or the fluidity retention is low. If the fluidity of the concrete becomes too high due to the post-addition of the admixture, the concrete causes material separation and the quality deteriorates.
本発明が解決しようとする課題は、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができるコンクリート用後添加混和剤を提供する処にある。 The problem to be solved by the present invention is that a post-added admixture for concrete that can maintain the fluidity of the concrete for a long time in a state immediately before the post-addition by post-adding to the prepared concrete that has not yet solidified It is in place to provide.
しかして本発明者らは、前記の課題を解決するべく研究した結果、コンクリート用後添加混和剤としては、分子中に特定の構成単位を有する共重合体の一つ又は二つ以上からなる特定のものが正しく好適であることを見出した。 Accordingly, as a result of studies conducted by the present inventors to solve the above-described problems, the post-additive admixture for concrete is specified as one or more of copolymers having specific structural units in the molecule. Was found to be correct and suitable.
すなわち本発明は、調製したまだ固まっていないコンクリートに後添加するコンクリート用後添加混和剤であって、全構成単位中に、８０〜９９．５質量％の下記の構成単位Ａと、０．５〜２０質量％の下記の構成単位Ｂと、０〜１０質量％の下記の構成単位Ｃとから構成された共重合体の一つ又は二つ以上から成り、且つ全体の酢酸換算含有割合が０．１〜４．０質量％であるものから成ることを特徴とするコンクリート用後添加混和剤に係る。 That is, the present invention is a post-additive admixture for concrete to be post-added to the prepared concrete that has not yet been set, and 80 to 99.5 mass% of the following structural unit A and 0.5 It consists of one or two or more of the copolymers comprised from the following structural unit B of -20 mass% and the following structural unit C of 0-10 mass%, and the whole acetic acid conversion content rate is 0. It relates to a post-additive admixture for concrete, characterized in that it is composed of from 0.1 to 4.0 mass%.
構成単位Ａ：下記の化１で示される単量体から選ばれる一つ又は二つ以上から形成された構成単位 Structural unit A: a structural unit formed from one or more selected from monomers represented by the following chemical formula 1
構成単位Ｂ：（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸及びそれらの塩から選ばれる一つ又は二つ以上から形成された構成単位 Structural unit B: a structural unit formed of one or more selected from (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid and salts thereof
化１において、
Ｒ１：炭素数２〜５のアルケニル基、炭素数３又は４の不飽和アシル基
Ｒ２：水素原子、炭素数１〜２２のアルキル基又は炭素数１〜２２の脂肪族アシル基
Ａ：炭素数２〜４のオキシアルキレン基で構成された平均付加モル数１〜３００個の（ポリ）オキシアルキレン基
In chemical formula 1,
R 1 : an alkenyl group having 2 to 5 carbon atoms, an unsaturated acyl group having 3 or 4 carbon atoms R 2 : a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aliphatic acyl group having 1 to 22 carbon atoms A: carbon (Poly) oxyalkylene group having an average addition mole number of 1 to 300 composed of oxyalkylene groups of 2 to 4
構成単位Ｃ：（メタ）アリルスルホン酸、（メタ）アリルスルホン酸塩、アクリルアミド、メタクリルアミド、アクリロニトリル及び（メタ）アクリル酸エステルから選ばれる一つ又は二つ以上から形成された構成単位 Structural unit C: a structural unit formed from one or more selected from (meth) allylsulfonic acid, (meth) allylsulfonate, acrylamide, methacrylamide, acrylonitrile and (meth) acrylic acid ester
本発明に係るコンクリート用後添加混和剤（以下、単に本発明の後添加混和剤という）は、調製したまだ固まっていないコンクリートに後添加するもので、全構成単位中に、８０〜９９．５質量％の前記の構成単位Ａと、０．５〜２０質量％の前記の構成単位Ｂと、０〜１０質量％の前記の構成単位Ｃとから構成された共重合体の一つ又は二つ以上から成るものである。 The post-additive admixture for concrete according to the present invention (hereinafter simply referred to as the post-additive admixture of the present invention) is post-added to the prepared concrete that has not yet solidified, and is in the range of 80 to 99.5 in all constituent units. One or two copolymers composed of the structural unit A by mass%, the structural unit B by 0.5 to 20 mass%, and the structural unit C by 0 to 10 mass%. It consists of the above.
構成単位Ａを形成することとなる化１で示される単量体において、化１中のＲ１としては、１）ビニル基、アリル基、メタリル基、３−ブテニル基、２−メチル−１−ブテニル基、３−メチル−１−ブテニル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基等の炭素数２〜５のアルケニル基、２）アクリロイル基、メタクリロイル基等の炭素数３〜４の不飽和アシル基が挙げられる。なかでも化１中のＲ１としては、アリル基、メタリル基、３−メチル−１−ブテニル基、アクリロイル基、メタクリロイル基が好ましい。 In the monomer represented by Chemical Formula 1 that forms the structural unit A, R 1 in Chemical Formula 1 is 1) vinyl group, allyl group, methallyl group, 3-butenyl group, 2-methyl-1- C2-C5 alkenyl group such as butenyl group, 3-methyl-1-butenyl group, 2-methyl-3-butenyl group and 3-methyl-3-butenyl group, 2) carbon such as acryloyl group and methacryloyl group The unsaturated acyl group of number 3-4 is mentioned. Among them, R 1 in Chemical Formula 1 is preferably an allyl group, a methallyl group, a 3-methyl-1-butenyl group, an acryloyl group, or a methacryloyl group.
化１中のＲ２としては、１）水素原子、２）メチル基、エチル基、ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基、ヘンエイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、２−メチル−ペンチル基、２−エチル−ヘキシル基、２−プロピル−ヘプチル基、２−ブチル−オクチル基、２−ペンチル−ノニル基、２−ヘキシル−デシル基、２−ヘプチル−ウンデシル基、２−オクチル−ドデシル基、２−ノニル−トリデシル基、２−デシル−テトラデシル基、２−ウンデシル−ペンタデシル基、２−ドデシル−ヘキサデシル基等の炭素数１〜２２のアルキル基、３）ホルミル基、アセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、エイコセノイル基、オクタデセノイル基等の炭素数１〜２２の脂肪族アシル基が挙げられる。なかでも化１中のＲ２としては、水素原子、炭素数１〜４のアルキル基、炭素数１〜４の脂肪族アシル基が好ましい。 As R 2 in Chemical Formula 1, 1) hydrogen atom, 2) methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, 2-methyl-pentyl group, 2- Ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2-pentyl-nonyl group, 2-hexyl-decyl group, 2-heptyl-undecyl group, 2-octyl-dodecyl group, 2-nonyl -Tridecyl group, 2-decyl-tetradecyl group, 2-undecyl-pentadecyl Groups, alkyl groups having 1 to 22 carbon atoms such as 2-dodecyl-hexadecyl group, 3) formyl group, acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecane C1-C22 aliphatic acyl groups, such as a noyl group, an octadecanoyl group, a hexadecenoyl group, an eicosenoyl group, an octadecenoyl group, are mentioned. Among these, R 2 in Chemical Formula 1 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aliphatic acyl group having 1 to 4 carbon atoms.
化１中のＡとしては、１）炭素数２〜４のオキシアルキレン基、２）合計２〜３００個の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基が挙げられる。なかでも化１中のＡとしては、合計１〜１６０個のオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基が好ましい。 Examples of A in Chemical Formula 1 include 1) an oxyalkylene group having 2 to 4 carbon atoms, and 2) a polyoxyalkylene group composed of a total of 2 to 300 oxyalkylene units having 2 to 4 carbon atoms. Among these, as A in Chemical Formula 1, a (poly) oxyalkylene group composed of a total of 1 to 160 oxyethylene units and / or oxypropylene units is preferable.
以上説明した化１で示される単量体の具体例としては、α−アリル−ω−アセチル−（ポリ）オキシエチレン、α−アリル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタリル−ω−メトキシ−（ポリ）オキシエチレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、−メタリル−ω−アセチル−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ブトキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−（３−メチル−３−ブテニル）−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、α−アクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン等が挙げられる。 Specific examples of the monomer represented by Chemical Formula 1 described above include α-allyl-ω-acetyl- (poly) oxyethylene, α-allyl-ω-acetyl- (poly) oxyethylene (poly) oxypropylene, α-allyl-ω-hydroxy- (poly) oxyethylene, α-allyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methallyl-ω-hydroxy- (poly) oxyethylene, α-methallyl -Ω-methoxy- (poly) oxyethylene, α-methallyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, -methallyl-ω-acetyl- (poly) oxyethylene, α- (3-methyl- 3-butenyl) -ω-hydroxy- (poly) oxyethylene, α- (3-methyl-3-butenyl) -ω-butoxy- (poly) oxyethylene , Α- (3-methyl-3-butenyl) -ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α- (3-methyl-3-butenyl) -ω-acetyl- (poly) oxyethylene ( Poly) oxypropylene, hydroxyethyl acrylate, hydroxypropyl acrylate, α-acryloyl-ω-hydroxy- (poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene, α-acryloyl-ω-butoxy- ( Poly) oxyethylene, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene, α-methacryloyl-ω-methoxy- (poly) oxy Ethylene, α-methacryloyl-ω-butoxy- (poly) oxyethylene Len, α-acryloyl-ω-methoxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-hydroxy- (poly) oxyethylene (poly) oxypropylene, α-methacryloyl-ω-acetyl- (poly ) Oxyethylene (poly) oxypropylene and the like.
化１で示される単量体としては、以上例示した単量体の一つ又は二つ以上を用いることができるが、なかでもヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを含むものを用いるのが好ましく、化１で示される単量体中にヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを３〜３０質量％含むものがより好ましい。 As the monomer represented by Chemical Formula 1, one or more of the monomers exemplified above can be used, and among them, hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate are included. It is preferable to use those, and those containing 3 to 30% by mass of hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate in the monomer represented by Chemical Formula 1 are more preferable.
構成単位Ｂを形成することとなる単量体としては、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸及びそれらの塩が挙げられる。なかでも構成単位Ｂを形成することとなる単量体としては、（メタ）アクリル酸、マレイン酸、（メタ）アクリル酸塩、マレイン酸塩が好ましい。 Examples of the monomer that forms the structural unit B include (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, and salts thereof. Among these, as the monomer that forms the structural unit B, (meth) acrylic acid, maleic acid, (meth) acrylate, and maleate are preferable.
構成単位Ｂを形成することとなる単量体の塩としては、特に制限するものではないが、これには例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。 The salt of the monomer that forms the structural unit B is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, and alkaline earth salts such as calcium salt and magnesium salt. Examples thereof include metal salts, ammonium salts, amine salts such as diethanolamine salts and triethanolamine salts.
構成単位Ｃを形成することとなる単量体は、（メタ）アリルスルホン酸、（メタ）アリルスルホン酸塩、アクリルアミド、メタクリルアミド、アクリロニトリル、（メタ）アクリル酸エステルである。 Monomers that form the structural unit C are (meth) allylsulfonic acid, (meth) allylsulfonic acid salt, acrylamide, methacrylamide, acrylonitrile, and (meth) acrylic acid ester.
本発明の後添加混和剤として用いる共重合体は、構成単位Ａと構成単位Ｂを必須の構成単位とし、構成単位Ｃを任意の構成単位とするものである。かかる共重合体における構成単位Ａの含有割合は全構成単位中に８０〜９９．５質量％とし、また構成単位Ｂの含有割合は全構成単位中に０．５〜２０質量％とし、構成単位Ｃの含有割合は全構成単位中に０〜１０質量％とする。 The copolymer used as the post-additive admixture of the present invention has the structural unit A and the structural unit B as essential structural units, and the structural unit C as an arbitrary structural unit. The content of the structural unit A in the copolymer is 80 to 99.5% by mass in all the structural units, and the content of the structural unit B is 0.5 to 20% by mass in the total structural units. The content ratio of C is 0 to 10% by mass in all the structural units.
本発明の後添加混和剤は以上説明した共重合体の一つ又は二つ以上から成るものであるが、全体の酢酸換算含有割合が０．１〜４．０質量％、好ましくは０．１〜３．０質量％の共重合体から成るものである。本発明において、酢酸換算含有割合は、本発明の後添加混和剤を構成する共重合体に含まれるカルボキシル基及びその塩を電位差滴定して酢酸に換算したときの質量％であり、具体的には、共重合体の４０質量％水溶液をイオン交換水で２０倍に希釈した２質量％水溶液に塩酸水溶液を加えてｐＨ２としたものを電位差滴定装置に供し、これを濃度０．１モル／Ｌの水酸化カリウム水溶液で滴定したときの、第１当量点と第２当量点との間に消費された水酸化カリウムと同モルの酢酸の質量を求め、求めた酢酸の質量の元の共重合体の質量に対する割合を算出した値（質量％）である。本発明において、全体の酢酸換算含有割合は、本発明の後添加混和剤が一つの共重合体から成るものである場合には、該一つの共重合体の酢酸換算含有割合であり、また本発明の後添加混和剤が二つ以上の共重合体から成るものである場合には、該二つ以上の共重合体における各共重合体の酢酸換算含有割合の加重平均値である。 The post-additive admixture of the present invention comprises one or two or more of the above-described copolymers, but the total acetic acid content is 0.1 to 4.0% by mass, preferably 0.1 It is composed of ˜3.0 mass% copolymer. In the present invention, the acetic acid equivalent content ratio is mass% when converted into acetic acid by potentiometric titration of the carboxyl group and its salt contained in the copolymer constituting the post-additive admixture of the present invention, specifically Prepared by adding a hydrochloric acid aqueous solution to a 2% by weight aqueous solution obtained by diluting a 40% by weight aqueous solution of the copolymer 20 times with ion-exchanged water and adjusting the pH to 2 and supplying the resulting solution to a potentiometric titrator. The amount of acetic acid in the same mole as potassium hydroxide consumed between the first equivalent point and the second equivalent point when titrated with an aqueous potassium hydroxide solution was determined. It is the value (mass%) which calculated the ratio with respect to the mass of coalescence. In the present invention, the total acetic acid equivalent content ratio is the acetic acid equivalent content ratio of the one copolymer when the post-additive admixture of the present invention is composed of one copolymer. When the post-additive admixture of the invention is composed of two or more copolymers, it is a weighted average value of acetic acid equivalent content of each copolymer in the two or more copolymers.
本発明の後添加混和剤に用いる共重合体それ自体は、公知の方法で製造することができる。これには、溶媒に水を用いたラジカル重合、溶媒に有機溶媒を用いたラジカル重合、無溶媒のラジカル重合がある。ラジカル重合に用いるラジカル重合開始剤は、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過酸化物やアゾビスイソブチロニトリルのように、重合反応温度下において分解し、ラジカル発生するものであればその種類は特に制限されない。得られる共重合体の質量平均分子量を所望の範囲とするため、連鎖移動剤を使用することもできる。 The copolymer itself used for the post-addition admixture of the present invention can be produced by a known method. This includes radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and solvent-free radical polymerization. The radical polymerization initiator used for radical polymerization decomposes at the polymerization reaction temperature, such as peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, and azobisisobutyronitrile, generating radicals. If it does, the kind in particular will not be restrict | limited. In order to make the mass average molecular weight of the copolymer obtained into a desired range, a chain transfer agent can also be used.
本発明の後添加混和剤の使用に際しては、得られた共重合体を単独で使用することもできるし、異なる共重合体の二つ以上を混合して使用することもできる。共重合体の二つ以上を混合して使用する場合には、少なくとも一つの共重合体がヒドロキシエチル（メタ）アクリレート及び／又はヒドロキシプロピル（メタ）アクリレートを含む化１で示される単量体から形成された構成単位Ａを有することが好ましい。また本発明の後添加混和剤の使用に際しては、本発明の効果を損なわない範囲内で、凝結遅延剤、凝結促進剤、防錆剤、ＡＥ剤、消泡剤等を併用することもできる。 In using the post-additive admixture of the present invention, the obtained copolymer can be used alone, or two or more different copolymers can be mixed and used. When two or more copolymers are used as a mixture, at least one copolymer is selected from monomers represented by Chemical Formula 1 containing hydroxyethyl (meth) acrylate and / or hydroxypropyl (meth) acrylate. It is preferable to have the structural unit A formed. Moreover, when using the post-added admixture of the present invention, a setting retarder, a setting accelerator, a rust inhibitor, an AE agent, an antifoaming agent and the like can be used in combination as long as the effects of the present invention are not impaired.
本発明の後添加混和剤は、調製したまだ固まっていないコンクリートに後添加するものである。かかるコンクリートの構成材料に特に制限はなく、例えば結合材としては、１）普通ポルトランドセメント、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、低熱ポルトランドセメント等の各種ポルトランドセメント、２）高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメント、３）アルミナセメント等が挙げられる。また水／結合材比も特に制限はないが、水／結合材比は３０〜７０％のものが好ましく、３５〜６５％のものがより好ましい。更にかかるコンクリートの調製に使用する分散剤の種類にも特に制限はないが、分散剤としてはオキシカルボン酸やその塩、ポリカルボン酸系、リグニンスルホン酸系のものから選ばれる一つ又は二つ以上が好ましい。 The post-added admixture of the present invention is post-added to prepared concrete that has not yet set. There are no particular restrictions on the constituent material of such concrete. For example, as a binder, 1) various portland cements such as ordinary portland cement, early strong portland cement, medium heat portland cement, low heat portland cement, etc., 2) blast furnace cement, fly ash cement And various mixed cements such as silica fume cement, and 3) alumina cement. The water / binder ratio is not particularly limited, but the water / binder ratio is preferably 30 to 70%, more preferably 35 to 65%. Further, the type of the dispersant used for the preparation of such concrete is not particularly limited, but the dispersant is one or two selected from oxycarboxylic acid and salts thereof, polycarboxylic acid type, lignin sulfonic acid type. The above is preferable.
本発明の後添加混和剤の使用量は、調製したまだ固まっていないコンクリート中の結合材１００質量部に対し、固形分換算で、通常は０．０１〜１．０質量部、好ましくは０．０１〜０．５質量部、より好ましくは０．０２〜０．５質量部とする。 The amount of the post-additive admixture used in the present invention is usually 0.01 to 1.0 parts by mass, preferably 0.00, in terms of solid content with respect to 100 parts by mass of the binder in the prepared concrete that has not yet solidified. 01 to 0.5 parts by mass, more preferably 0.02 to 0.5 parts by mass.
本発明によると、調製したまだ固まっていないコンクリートに後添加することによって、コンクリートの流動性を、増大させることなく、後添加直前の状態に長時間にわたって保持することができる。 According to the present invention, by post-adding to the prepared concrete which has not yet been solidified, the fluidity of the concrete can be maintained for a long time without increasing the concrete flow.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（共重合体の合成）
・共重合体（Ｓ−１）の合成
イオン交換水７６．６ｇ及びα−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝１１５、ｎはオキシエチレン単位の数、以下同じ）オキシエチレン１５６．４ｇを、温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器（以下、同様のものを使用した）に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。次に１％過酸化水素水８．８ｇを３時間かけて滴下し、またそれと同時に、イオン交換水３９．１ｇにヒドロキシエチルアクリレート１５．６ｇとアクリル酸３．９ｇとアクリル酸メチル１９．５ｇを均一に溶解させた水溶液を３時間かけて滴下し、更にそれと同時に、イオン交換水７．０ｇにＬ−アスコルビン酸０．８ｇとチオグリコール酸１．０ｇを溶解させた水溶液を４時間かけて滴下した。その後６５℃で２時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−１）の４０％水溶液を得た。
Test Category 1 (Synthesis of copolymer)
Synthesis of copolymer (S-1) 76.6 g of ion-exchanged water and α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 115, n is the number of oxyethylene units, and so on. ) Charge 156.4 g of oxyethylene into a reaction vessel (hereinafter, the same one is used) equipped with a thermometer, stirrer, dropping funnel and nitrogen introducing tube, dissolve uniformly with stirring, and then add nitrogen to the atmosphere. The temperature of the reaction system was set to 65 ° C. with a warm water bath. Next, 8.8 g of 1% hydrogen peroxide solution was added dropwise over 3 hours. At the same time, 15.6 g of hydroxyethyl acrylate, 3.9 g of acrylic acid and 19.5 g of methyl acrylate were added to 39.1 g of ion-exchanged water. A uniformly dissolved aqueous solution was added dropwise over 3 hours, and at the same time, an aqueous solution prepared by dissolving 0.8 g of L-ascorbic acid and 1.0 g of thioglycolic acid in 7.0 g of ion-exchanged water was added dropwise over 4 hours. did. Thereafter, the polymerization reaction was completed by maintaining at 65 ° C. for 2 hours. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution is added to adjust the reaction system to pH 6, and the concentration is adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-1). It was.
・共重合体（Ｓ−２）の合成
イオン交換水７８．０ｇを反応容器に仕込み、攪拌しながら雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃とした。イオン交換水１４１．７ｇ、α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレン１４７．８ｇ、ヒドロキシエチルアクリレート４５．３ｇ、メタクリル酸３．９ｇ及びメルカプトエタノール１．４ｇを均一に溶解させた水溶液を２時間かけて滴下すると共に、１０％過硫酸アンモニウム２８．６ｇを３時間かけて滴下した。その後６５℃で１時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体１（Ｓ−２）の４０％水溶液を得た。
-Synthesis | combination of copolymer (S-2) 78.0g of ion-exchange water was prepared to reaction container, atmosphere was substituted with nitrogen, stirring, and the temperature of the reaction system was 65 degreeC with the hot water bath. 141.7 g of ion-exchanged water, 147.8 g of α-methacryloyl-ω-methoxy-poly (n = 9) oxyethylene, 45.3 g of hydroxyethyl acrylate, 3.9 g of methacrylic acid and 1.4 g of mercaptoethanol are uniformly dissolved. The aqueous solution was added dropwise over 2 hours, and 28.6 g of 10% ammonium persulfate was added dropwise over 3 hours. Thereafter, the polymerization reaction was completed by maintaining at 65 ° C. for 1 hour. After completion of the polymerization reaction, a 30% aqueous sodium hydroxide solution is added to adjust the reaction system to pH 6, the concentration is adjusted to 40% with ion-exchanged water, and a 40% aqueous solution of copolymer 1 (S-2) is prepared. Obtained.
・共重合体（Ｓ−３）の合成
イオン交換水２８．１ｇ、α−（メタリル）−ω−ヒドロキシ−ポリ（ｎ＝５３）オキシエチレン１５６．３ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて７０℃とした。次に５％過酸化水素水溶液６．９ｇを３時間かけて滴下し、またそれと同時に、イオン交換水１５６．３ｇにヒドロキシエチルアクリレート３７．９ｇとアクリル酸１．２ｇを均一に溶解させた水溶液を３時間かけて滴下し、更にそれと同時に、イオン交換水５．５ｇにＬ−アスコルビン酸０．８ｇと３−メルカプトプロピオン酸０．６ｇを溶解させた水溶液を３時間かけて滴下した。その後７０℃で１時間維持し、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えてｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−３）の４０％水溶液で得た。
-Synthesis of copolymer (S-3) Charged 28.1 g of ion-exchanged water and 156.3 g of α- (methallyl) -ω-hydroxy-poly (n = 53) oxyethylene into a reaction vessel and stirred uniformly. After dissolution, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70 ° C. in a warm water bath. Next, 6.9 g of a 5% hydrogen peroxide aqueous solution was dropped over 3 hours, and at the same time, an aqueous solution in which 37.9 g of hydroxyethyl acrylate and 1.2 g of acrylic acid were uniformly dissolved in 156.3 g of ion-exchanged water. The solution was added dropwise over 3 hours, and at the same time, an aqueous solution prepared by dissolving 0.8 g of L-ascorbic acid and 0.6 g of 3-mercaptopropionic acid in 5.5 g of ion-exchanged water was added dropwise over 3 hours. Thereafter, the polymerization reaction was completed by maintaining at 70 ° C. for 1 hour. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-3).
・共重合体（Ｓ−４）の合成
イオン交換水２１４．０ｇ、α−メタクリロイル−ω−ヒドロキシ−ポリ（ｎ＝２１）オキシエチレンポリ（ｍ＝２、ｍはオキシプロピレン単位の数、以下同じ）オキシプロピレン１４７．１ｇ、メタクリル酸３４．４ｇ、アクリル酸ブチル９．６ｇ及び３−メルカプトプロピオン酸１．５ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて６０℃に保ち、１０％過硫酸ナトリウム水溶液２７．７ｇを４時間かけて投入した。更に６０℃で２時間保持して、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−４）の４０％水性液を得た。
-Synthesis of copolymer (S-4) 214.0 g of ion-exchanged water, α-methacryloyl-ω-hydroxy-poly (n = 21) oxyethylene poly (m = 2, m is the number of oxypropylene units, and so on. ) 147.1 g of oxypropylene, 34.4 g of methacrylic acid, 9.6 g of butyl acrylate and 1.5 g of 3-mercaptopropionic acid were charged in a reaction vessel and dissolved uniformly with stirring, and then the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60 ° C. in a warm water bath, and 27.7 g of a 10% aqueous sodium persulfate solution was added over 4 hours. Further, the polymerization reaction was completed by maintaining at 60 ° C. for 2 hours. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-4).
・共重合体（Ｓ−５）の合成
イオン交換水２１５．４ｇ、α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレン１６６．９ｇ、メタクリル酸２４．９ｇ及び３−メルカプトプロピオン酸１．９ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて６０℃に保ち、１０％過硫酸ナトリウム水溶液２２．３ｇを投入した。６０℃で３時間保持した後、１０％過硫酸ナトリウム水溶液５．６ｇを加えた。更に６０℃で２時間保持して、重合反応を終了した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ６に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−５）の４０％水性液を得た。
Synthesis of copolymer (S-5) 215.4 g of ion exchange water, α-methacryloyl-ω-methoxy-poly (n = 9) oxyethylene 166.9 g, methacrylic acid 24.9 g and 3-mercaptopropionic acid 1 .9 g was charged into a reaction vessel and dissolved uniformly with stirring, and the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60 ° C. in a warm water bath, and 22.3 g of a 10% aqueous sodium persulfate solution was added. After maintaining at 60 ° C. for 3 hours, 5.6 g of a 10% aqueous sodium persulfate solution was added. Further, the polymerization reaction was completed by maintaining at 60 ° C. for 2 hours. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-5).
・共重合体（Ｓ−６）の合成
無水マレイン酸１４７ｇ及びα−アリル−ω−メトキシ−ポリ（ｎ＝５０）オキシエチレン１５２７ｇを反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて８０℃に保ち、アゾビスイソブチロニトリル１０．０ｇを投入して、ラジカル共重合反応を開始した。１時間後、更にアゾビスイソブチロニトリル５．０ｇを投入し、その１時間後、更にアゾビスイソブチロニトリル５．０ｇを投入して、５時間ラジカル共重合反応を行なった後、反応系にイオン交換水３００ｇを加えてラジカル共重合反応を停止した。その後、３０％水酸化ナトリウム水溶液を加えて反応系をｐＨ５に調整し、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ−６）の４０％水溶液を得た。
Synthesis of copolymer (S-6) 147 g of maleic anhydride and 1527 g of α-allyl-ω-methoxy-poly (n = 50) oxyethylene were charged in a reaction vessel and dissolved uniformly with stirring, and then the atmosphere was changed. Replaced with nitrogen. The temperature of the reaction system was kept at 80 ° C. in a warm water bath, and 10.0 g of azobisisobutyronitrile was added to start radical copolymerization reaction. After 1 hour, 5.0 g of azobisisobutyronitrile was added, and after 1 hour, 5.0 g of azobisisobutyronitrile was further added, and a radical copolymerization reaction was performed for 5 hours. 300 g of ion exchange water was added to the system to stop the radical copolymerization reaction. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust the reaction system to pH 5, and the concentration was adjusted to 40% with ion-exchanged water to obtain a 40% aqueous solution of copolymer (S-6).
・共重合体（Ｓ−７）の合成
特開２００７―１１９３３７号公報の段落「００６７」に記載された製造例１の方法で製造を行い、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ―７）の４０％水溶液を得た。
-Synthesis of copolymer (S-7) The copolymer (S-7) was prepared by the method of Production Example 1 described in paragraph "0067" of JP-A No. 2007-119337, and the concentration was adjusted to 40% with ion-exchanged water. A 40% aqueous solution of copolymer (S-7) was obtained.
・共重合体（Ｓ−８）の合成
特開２０１１―０２６１６７号公報の段落「００２５」に記載された方法で製造を行い、イオン交換水にて濃度を４０％に調整して、共重合体（Ｓ―８）の４０％水溶液を得た。
-Synthesis of copolymer (S-8) Manufactured by the method described in paragraph "0025" of JP2011-026167A, adjusted to a concentration of 40% with ion-exchanged water, and copolymer A 40% aqueous solution of (S-8) was obtained.
製造した各共重合体の質量平均分子量をゲルパーミエーションクロマトグラフィーにて測定すると共に、酢酸換算含有割合を前記の方法にて測定した。各共重合体の内容及び測定結果を表１にまとめて示した。 While measuring the mass mean molecular weight of each manufactured copolymer by gel permeation chromatography, the acetic acid conversion content rate was measured by the said method. The contents and measurement results of each copolymer are summarized in Table 1.
表１において、
Ａ−１：α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝１１５）オキシエチレンから形成された構成単位
Ａ−２：α−メタクリロイル−ω−メトキシ−ポリ（ｎ＝９）オキシエチレンから形成された構成単位
Ａ−３：α−メタリル−ω−ヒドロキシ−ポリ（ｎ＝５３）オキシエチレンから形成された構成単位
Ａ−４：α−メタクリロイル−ω−ヒドロキシ−ポリ（ｎ＝２１）オキシエチレンポリ（ｍ＝２、ｍはオキシプロピレン単位の数、以下同じ）オキシプロピレンから形成された構成単位
Ａ−５：α−アリル−ω−メトキシ−ポリ（ｎ＝５０）オキシエチレンから形成された構成単位
Ａ−６：ヒドロキシエチルアクリレートから形成された構成単位
Ａ−７：α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−ポリ（ｎ＝５０）オキシエチレンから形成された構成単位
Ａ−８：α−アリル−ω−メトキシ−ポリ（ｎ＝３３）オキシエチレンから形成された構成単位
Ｂ−１：アクリル酸から形成された構成単位
Ｂ−２：メタクリル酸から形成された構成単位
Ｂ−３：マレイン酸から形成された構成単位
Ｃ−１：アクリル酸メチルから形成された構成単位
Ｃ−２：アクリル酸ブチルから形成された構成単位
In Table 1,
A-1: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 115) structural unit formed from oxyethylene A-2: α-methacryloyl-ω-methoxy-poly (n = 9) Structural unit formed from oxyethylene A-3: α-methallyl-ω-hydroxy-poly (n = 53) Structural unit formed from oxyethylene A-4: α-methacryloyl-ω-hydroxy-poly ( n = 21) Oxyethylene poly (m = 2, m is the number of oxypropylene units, the same shall apply hereinafter) A structural unit formed from oxypropylene A-5: α-allyl-ω-methoxy-poly (n = 50) oxy Structural unit formed from ethylene A-6: Structural unit formed from hydroxyethyl acrylate A-7: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n 50) Structural unit formed from oxyethylene A-8: Structural unit formed from α-allyl-ω-methoxy-poly (n = 33) oxyethylene B-1: Structural unit formed from acrylic acid B- 2: Structural unit formed from methacrylic acid
B-3: Structural unit formed from maleic acid
C-1: Structural unit formed from methyl acrylate C-2: Structural unit formed from butyl acrylate
試験区分２（後添加混和剤の調製）
・実施例１（後添加混和剤（Ｐ−１）の調製）
前記の共重合体（Ｓ−３）をそのまま後添加混和剤（Ｐ−１）とした。したがって全体の酢酸換算含有割合は０．７％である。使用に際しては、前記の共重合体（Ｓ−３）の水溶液を更にイオン交換水で希釈して２０％水溶液とした。
Test Category 2 (Preparation of post-additive admixture)
Example 1 (Preparation of post-added admixture (P-1))
The copolymer (S-3) was directly used as a post-additive admixture (P-1). Therefore, the total acetic acid content is 0.7%. In use, the aqueous solution of the copolymer (S-3) was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例２（後添加混和剤（Ｐ−２）の調製）
前記の共重合体（Ｓ−１）をそのまま後添加混和剤（Ｐ−２）とした。したがって全体の酢酸換算含有割合は１．７％である。使用に際しては、前記の共重合体（Ｓ−１）の水溶液を更にイオン交換水で希釈して２０％水溶液とした。
Example 2 (Preparation of post-added admixture (P-2))
The copolymer (S-1) was used as the post-added admixture (P-2) as it was. Therefore, the total acetic acid equivalent content is 1.7%. In use, the aqueous solution of the copolymer (S-1) was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例３（後添加混和剤（Ｐ−３）の調製）
前記の共重合体（Ｓ−２）が９０部及び前記の共重合体（Ｓ−４）が１０部の割合となるように均一混合したものを後添加混和剤（Ｐ−３）とした。したがって全体の酢酸換算含有割合は２．５％である。使用に際しては、前記の双方の水溶液の混合液を更にイオン交換水で希釈して２０％水溶液とした。
Example 3 (Preparation of post-added admixture (P-3))
What was uniformly mixed so that the copolymer (S-2) was 90 parts and the copolymer (S-4) was 10 parts was used as a post-added admixture (P-3). Therefore, the total acetic acid equivalent content is 2.5%. In use, the mixture of both aqueous solutions was further diluted with ion-exchanged water to obtain a 20% aqueous solution.
・実施例４〜６（後添加混和剤（Ｐ−４）〜（Ｐ−６）の調製）
実施例３の後添加混和剤（Ｐ−３）の場合と同様にして、表２に記載の内容で、後添加混和剤（Ｐ−４）〜（Ｐ−６）を調製した。
Examples 4 to 6 (Preparation of post-added admixtures (P-4) to (P-6))
In the same manner as in the case of the post-additive admixture (P-3) of Example 3, post-addition admixtures (P-4) to (P-6) were prepared with the contents shown in Table 2.
・比較例１〜６（後添加混和剤（Ｒ−１）〜（Ｒ−６）、（Ｒ−９）及び（Ｒ−１０）の調製）
実施例１、２又は３の後添加混和剤（Ｐ−１）、（Ｐ−２）又は（Ｐ−３）の場合と同様にして、表２に記載の内容で、後添加混和剤（Ｒ−１）〜（Ｒ−６）、（Ｒ−９）、（Ｒ―１０）を調製した。
Comparative Examples 1 to 6 (Preparation of post-added admixtures (R-1) to (R-6), (R-9) and (R-10))
In the same manner as in the case of the post-additive admixture (P-1), (P-2) or (P-3) of Examples 1, 2, or 3, the post-additive admixture (R -1) to (R-6), (R-9) and (R-10) were prepared.
・比較例７（後添加混和剤（Ｒ−７）の調製）
凝結遅延剤として市販されているポリヒドロキシカルボン酸複合体（竹本油脂社製の凝結遅延剤Ｔ−２１）をそのまま後添加混和剤（Ｒ−７）とした。使用に際してはイオン交換水で水希釈して２０％水溶液とした。
Comparative Example 7 (Preparation of post-added admixture (R-7))
A polyhydroxycarboxylic acid complex (setting retarder T-21 manufactured by Takemoto Yushi Co., Ltd.) commercially available as a setting retarder was used as the post-added admixture (R-7). At the time of use, it was diluted with ion-exchanged water to make a 20% aqueous solution.
・比較例８（後添加混和剤（Ｒ−８）の調製）
流動化剤として市販されているアルキルアリルスルホン酸塩高縮合物（竹本油脂社製の流動化剤ハイフルード）をそのまま後添加混和剤（Ｒ−８）とした。使用に際してはイオン交換水で水希釈して２０％水溶液とした。
Comparative Example 8 (Preparation of post-added admixture (R-8))
Alkyl allyl sulfonate high condensate commercially available as a fluidizing agent (Fluidizing agent fluid made by Takemoto Yushi Co., Ltd.) was used as it was as a post-additive admixture (R-8). At the time of use, it was diluted with ion-exchanged water to make a 20% aqueous solution.
以上で調製した各例の後添加混和剤（Ｐ−１）〜（Ｐ−６）及び（Ｒ−１）〜（Ｒ−８）の内容を表２にまとめて示した。
The contents of the post-added admixtures (P-1) to (P-6) and (R-1) to (R-8) of each example prepared above are summarized in Table 2.
表２において、
比較例７及び８：構成単位Ａ及びＢを有する構造のものではない。
In Table 2,
Comparative Examples 7 and 8: The structure does not have the structural units A and B.
試験区分３（コンクリートの調製、後添加混和剤の後添加及び評価）
・コンクリートの調製
５５Ｌの強制二軸ミキサーに、表３に記載の内容で、普通ポルトランドセメント（太平洋セメント社製、比重＝３．１６）、細骨材（大井川水系砂、比重＝２．５８）及び粗骨材（岡崎産砕石、比重＝２．６８）を順次投入して５秒間空練りした後、目標スランプフローが１５±２．５ｃｍ及び空気量が４．５±０．５％の範囲となるよう、ＡＥ減水剤（竹本油脂社製の商品名チューポールＥＸ２０）をセメントに対し１％、ＡＥ剤（竹本油脂社製の商品名ＡＥ−３００）をセメントに対し０．００５％及び消泡剤（竹本油脂社製の商品名ＡＦＫ−２）をセメントに対し０．００１％となるよう練混ぜ水と共に投入し、９０秒間練混ぜて、コンクリートを調製した。このコンクリートを用い、温度２０±３℃、湿度６０％の雰囲気下にて、以下のように試験を行なった。結果を表４及び表５にまとめて示した。
Test category 3 (preparation of concrete, post-addition of post-additives and evaluation)
・ Preparation of concrete In 55L forced biaxial mixer, with the contents shown in Table 3, ordinary Portland cement (manufactured by Taiheiyo Cement, specific gravity = 3.16), fine aggregate (Oikawa water sand, specific gravity = 2.58) And after adding coarse aggregate (Okazaki crushed stone, specific gravity = 2.68) sequentially and kneading for 5 seconds, the target slump flow is 15 ± 2.5cm and the air volume is in the range of 4.5 ± 0.5% 1% of AE water-reducing agent (trade name Tupole EX20 manufactured by Takemoto Yushi Co., Ltd.) for cement, 0.005% for AE agent (trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.) A foaming agent (trade name AFK-2 manufactured by Takemoto Yushi Co., Ltd.) was added together with mixing water so as to be 0.001% with respect to cement, and was mixed for 90 seconds to prepare concrete. Using this concrete, the test was performed as follows in an atmosphere of a temperature of 20 ± 3 ° C. and a humidity of 60%. The results are summarized in Table 4 and Table 5.
練混ぜ直後から２０分静置の時点で、コンクリートに後添加混和剤（Ｐ−１）〜（Ｐ−６）及び（Ｒ−１）〜（Ｒ−１０）を添加し（但し、試験例１０は未添加のブランク）、３０秒間練混ぜ、静置した。練混ぜ直後から３０分間隔で、静置したコンクリートのスランプを測定し、また２４時間静置後の硬化体のブリーディング率及び圧縮強度を次のように測定した。 At the time of standing for 20 minutes immediately after kneading, post-additives (P-1) to (P-6) and (R-1) to (R-10) were added to the concrete (however, Test Example 10) Was blank with no addition), mixed for 30 seconds and allowed to stand. The slump of the concrete that was allowed to stand was measured at intervals of 30 minutes immediately after mixing, and the bleeding rate and compressive strength of the cured product after being allowed to stand for 24 hours were measured as follows.
・スランプ：ＪＩＳ−Ａ１１５０に準拠して測定した。
・ブリーディング：ＪＩＳ−Ａ１１２３に準拠して測定した。
・圧縮強度：ＪＩＳ−Ａ１１０８に準拠し、供試体寸法を直径１００ｍｍ×長さ２００ｍｍとし、材齢２４時間で測定した。
-Slump: Measured according to JIS-A1150.
-Bleeding: Measured according to JIS-A1123.
-Compressive strength: Based on JIS-A1108, the specimen size was 100 mm in diameter x 200 mm in length, and measured at a material age of 24 hours.
表４において、
添加量：セメントに対する後添加混和剤の添加量（％）
＊１：コンクリートの練混ぜ直後から２０分、５０分、８０分経過の各時点で後添加混和剤を０．１％ずつ後添加し、合計０．３％添加した。
＊２：コンクリートの練混ぜ直後から１０分経過の時点で後添加混和剤を０．３％後添加した。
＊３：後添加混和剤の後添加を行わなかった。
In Table 4,
Addition amount: Addition amount of post-additive admixture to cement (%)
* 1: After each of 20 minutes, 50 minutes, and 80 minutes after the concrete was mixed, the post-added admixture was added by 0.1%, and a total of 0.3% was added.
* 2: After 10 minutes from immediately after mixing the concrete, the post-added admixture was added after 0.3%.
* 3: After-addition admixture was not added afterwards.
表５において、
＊４：硬化体が圧縮強度を測定できる強度に到達していなかった。
In Table 5,
* 4: The cured product did not reach the strength at which the compressive strength could be measured.
図１は本発明の後添加混和剤等を後添加したコンクリートのスランプの変化を例示するグラフである。横軸に後添加混和剤等を加えた直後からの時間（分）を目盛り、また縦軸にスランプ（ｃｍ）を目盛っている。図１中、１は試験例１についてのスランプの変化を示す折れ線、１０は試験例１０についてのスランプの変化を示す折れ線（但し、試験例１０は後添加混和剤を未添加）、１５は試験例１５についてのスランプの変化を示す折れ線、１９は試験例１９についてのスランプの変化を示す折れ線である。 FIG. 1 is a graph illustrating the change in the slump of concrete to which the post-added admixture or the like of the present invention is post-added. The horizontal axis indicates the time (minutes) immediately after the addition of the post-added admixture and the like, and the vertical axis indicates the slump (cm). In FIG. 1, 1 is a polygonal line showing the change in slump for Test Example 1, 10 is a polygonal line showing the change in slump for Test Example 10 (however, Test Example 10 has no post-added admixture added), and 15 is the test. A polygonal line indicating the change in the slump for the example 15 and 19 is a polygonal line indicating the change in the slump for the test example 19.
表１〜表３に対応する表４及び表５の結果、更には図１の結果からも明らかなように、本発明の後添加混和剤によると、調製したまだ固まっていないコンクリートに後添加することによって、得られる硬化体のブリーディング率や圧縮強度に悪影響を及ぼすことなく、コンクリートの流動性を、後添加直前の状態に長時間にわたって保持することができる。 As is apparent from the results of Tables 4 and 5 corresponding to Tables 1 to 3 and also from the results of FIG. 1, according to the post-additive of the present invention, the post-addition is performed on the prepared concrete that has not yet solidified. Thus, the fluidity of the concrete can be maintained for a long time in the state immediately before post-addition without adversely affecting the bleeding rate and compressive strength of the obtained cured product.
１ 試験例１についてのスランプの変化を示す折れ線
１０ 試験例１０についてのスランプの変化を示す折れ線
１５ 試験例１５についてのスランプの変化を示す折れ線
１９ 試験例１９についてのスランプの変化を示す折れ線
DESCRIPTION OF SYMBOLS 1 Broken line which shows the change of slump about Test Example 1 10 Broken line which shows the change of slump about Test Example 10 15 Broken line which shows the change of slump about Test Example 15 19 Broken line which shows the change of slump about Test Example 19
Claims (7)
構成単位Ａ：下記の化１で示される単量体から選ばれる一つ又は二つ以上から形成された構成単位
構成単位Ｂ：（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸及びそれらの塩から選ばれる一つ又は二つ以上から形成された構成単位
Ｒ１：炭素数２〜５のアルケニル基又は炭素数３〜４の不飽和アシル基
Ｒ２：水素原子、炭素数１〜２２のアルキル基又は炭素数１〜２２の脂肪族アシル基
Ａ：炭素数２〜４のオキシアルキレン基で構成された平均付加モル数１〜３００個の（ポリ）オキシアルキレン基）A post-additive admixture for concrete to be added to the prepared concrete that has not yet solidified, comprising the following structural unit A, the following structural unit B, and other components in the range of 0 to 20% by mass of the total structural units For concrete, comprising one or more copolymers composed of the structural unit C and having a total acetic acid equivalent content of 0.1 to 4.0% by mass Post-added admixture.
Structural unit A: Structural unit formed from one or more selected from monomers represented by the following chemical formula 1 Structural unit B: (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) ) A structural unit formed of one or more selected from itaconic acid and salts thereof
R 1 : an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 to 4 carbon atoms R 2 : a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aliphatic acyl group having 1 to 22 carbon atoms A: carbon (Poly) oxyalkylene group having an average addition mole number of 1 to 300 composed of oxyalkylene groups of 2 to 4)
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| JP7303525B2 (en) * | 2020-01-09 | 2023-07-05 | 株式会社大林組 | ADDITIVE FOR HYDRAULIC COMPOSITION, AND HYDRAULIC COMPOSITION |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63156049A (en) * | 1986-07-31 | 1988-06-29 | 藤沢薬品工業株式会社 | Concrete admixing agent |
| JPH11322391A (en) * | 1998-05-20 | 1999-11-24 | Denka Grace Kk | Cement dispersant |
| JP2001220194A (en) * | 2000-02-02 | 2001-08-14 | Lion Corp | Mixing agent for cement |
| JP2007119337A (en) * | 2005-09-28 | 2007-05-17 | Nippon Shokubai Co Ltd | Cement admixture and cement composition |
| JP2009173527A (en) * | 2007-12-28 | 2009-08-06 | Kao Corp | Hydraulic composition |
| JP2009263181A (en) * | 2008-04-28 | 2009-11-12 | Takemoto Oil & Fat Co Ltd | Cement dispersant and cement composition |
| JP2011026167A (en) * | 2009-07-24 | 2011-02-10 | Takemoto Oil & Fat Co Ltd | Fluidizing agent for preparing high strength soil cement slurry and method for preparing high strength soil cement slurry |
-
2015
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63156049A (en) * | 1986-07-31 | 1988-06-29 | 藤沢薬品工業株式会社 | Concrete admixing agent |
| JPH11322391A (en) * | 1998-05-20 | 1999-11-24 | Denka Grace Kk | Cement dispersant |
| JP2001220194A (en) * | 2000-02-02 | 2001-08-14 | Lion Corp | Mixing agent for cement |
| JP2007119337A (en) * | 2005-09-28 | 2007-05-17 | Nippon Shokubai Co Ltd | Cement admixture and cement composition |
| JP2009173527A (en) * | 2007-12-28 | 2009-08-06 | Kao Corp | Hydraulic composition |
| JP2009263181A (en) * | 2008-04-28 | 2009-11-12 | Takemoto Oil & Fat Co Ltd | Cement dispersant and cement composition |
| JP2011026167A (en) * | 2009-07-24 | 2011-02-10 | Takemoto Oil & Fat Co Ltd | Fluidizing agent for preparing high strength soil cement slurry and method for preparing high strength soil cement slurry |
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