JP2021109797A - Additive for hydraulic composition, and hydraulic composition - Google Patents
Additive for hydraulic composition, and hydraulic composition Download PDFInfo
- Publication number
- JP2021109797A JP2021109797A JP2020001783A JP2020001783A JP2021109797A JP 2021109797 A JP2021109797 A JP 2021109797A JP 2020001783 A JP2020001783 A JP 2020001783A JP 2020001783 A JP2020001783 A JP 2020001783A JP 2021109797 A JP2021109797 A JP 2021109797A
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- Prior art keywords
- component
- mass
- structural unit
- additive
- hydraulic composition
- Prior art date
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- Granted
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- 239000000654 additive Substances 0.000 title claims abstract description 61
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- 150000004044 tetrasaccharides Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000004043 trisaccharides Chemical class 0.000 description 1
- RULSWEULPANCDV-PIXUTMIVSA-N turanose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](C(=O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RULSWEULPANCDV-PIXUTMIVSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- FYGDTMLNYKFZSV-BYLHFPJWSA-N β-1,4-galactotrioside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-BYLHFPJWSA-N 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、水硬性組成物用添加剤、及び水硬性組成物に関する。更に詳しくは、３５℃以上の高温環境下でコンクリート等の水硬性組成物を使用する場合であっても、２５℃未満の標準環境下での使用と同等のスランプ保持性、凝結時間、及びブリーディング率の発現を可能とする性能を備えた、水硬性組成物の調製と同時に添加される同時添加型の水硬性組成物用添加剤、及び当該水硬性組成物用添加剤を添加した水硬性組成物に関する。 The present invention relates to an additive for a hydraulic composition and a hydraulic composition. More specifically, even when a hydraulic composition such as concrete is used in a high temperature environment of 35 ° C. or higher, slump retention, setting time, and bleeding equivalent to those used in a standard environment of less than 25 ° C. A simultaneous addition type additive for a hydraulic composition, which is added at the same time as the preparation of the hydraulic composition, and a hydraulic composition to which the additive for the hydraulic composition is added, which has a performance capable of expressing the rate. Regarding things.
水硬性組成物は、セメントペースト、モルタル、コンクリートなどのセメント組成物として広く用いられている。これらの水硬性組成物（例えば、コンクリート）は、一般にコンクリート製造工場において、各種材料を練り混ぜて調製された後、流動性を保った状態で使用場所（施工現場）までコンクリートミキサー車によって運搬し、使用されている。 The hydraulic composition is widely used as a cement composition such as cement paste, mortar, and concrete. These hydraulic compositions (for example, concrete) are generally prepared by kneading various materials in a concrete manufacturing factory, and then transported to the place of use (construction site) while maintaining fluidity by a concrete mixer truck. ,in use.
このとき、交通渋滞やその他要因によって製造工場から使用場所への運搬に時間を要すると、調製されたコンクリートの流動性が低下し、使用場所でのコンクリートの打ち込み作業が困難になることがある。そのため、調製された未硬化の状態のコンクリートに後添加し、コンクリートの流動性を長時間に亘って保持するための後添加混和剤等が既に提案されている（例えば、特許文献１参照）。 At this time, if it takes time to transport the prepared concrete from the manufacturing factory to the place of use due to traffic congestion or other factors, the fluidity of the prepared concrete may decrease, and the concrete driving work at the place of use may become difficult. Therefore, a post-addition admixture or the like for post-adding to the prepared uncured concrete to maintain the fluidity of the concrete for a long period of time has already been proposed (see, for example, Patent Document 1).
一方、オキシカルボン酸またはその塩から構成された凝結遅延剤、及び、アミノスルホン酸等の化合物から構成された高性能ＡＥ減水剤によって構成され、コンクリートまたはモルタルの初期スランプを長時間にわたって維持するための初期スランプ長時間維持剤を使用することも既に提案されている（例えば、特許文献２参照）。 On the other hand, it is composed of a setting retarder composed of oxycarboxylic acid or a salt thereof and a high-performance AE water reducing agent composed of a compound such as aminosulfonic acid, in order to maintain the initial slump of concrete or mortar for a long period of time. It has already been proposed to use the initial slump long-term maintenance agent of (see, for example, Patent Document 2).
また、第一及び第二のポリカルボキシレートポリエーテル櫛形ポリマー超可塑剤を含み、第一の混合物系組成物によって初期スランプ向上、後期スランプ維持、及び初期スランプの制限を達成し、第二の混合物により後期スランプ向上を達成するものも知られている（例えば、特許文献３参照）。これらによって、コンクリート等の初期スランプを数日間という長時間にわたり維持させることができる。 It also contains first and second polycarboxylate polyether comb-shaped polymer thermoplastics, the first mixture-based composition achieves early slump enhancement, late slump maintenance, and early slump limits, the second mixture. It is also known that the late slump improvement is achieved by the above (see, for example, Patent Document 3). As a result, the initial slump such as concrete can be maintained for a long period of several days.
上記のように、調製されたコンクリート等の水硬性組成物の流動性を維持するための混和剤等は既に提案されている。ここで、コンクリート等の水硬性組成物の流動性に及ぼす要因として、施工時における水硬性組成物の温度や、施工時の周囲の温度が大きいことが知られている。特に３５℃以上の高温環境下では、水硬性組成物に含まれるセメントの水和反応が促進されることにより、スランプロスが増大したり、凝結が促進されたりするなどの問題を生じることがあった。そのため、コンクリートの施工に悪影響を及ぼし、施工不良等の不具合を生じさせる可能性があった。 As described above, admixtures and the like for maintaining the fluidity of the prepared hydraulic composition such as concrete have already been proposed. Here, it is known that the temperature of the hydraulic composition at the time of construction and the ambient temperature at the time of construction are large as factors affecting the fluidity of the hydraulic composition such as concrete. In particular, in a high temperature environment of 35 ° C. or higher, the hydration reaction of cement contained in the hydraulic composition is promoted, which may cause problems such as increased slump loss and accelerated coagulation. rice field. Therefore, there is a possibility that the construction of concrete may be adversely affected and problems such as poor construction may occur.
特に近年において、夏期に日中最高気温が３５℃以上の猛暑日となる日数が増大しており、コンクリートの施工作業を中止したり、或いは施工時間を変更したりするなどの対応や、水硬性組成物の温度が３５℃を超えないような対策を施したりするなどの対応が必要となることがあった。 Especially in recent years, the number of days when the maximum daytime temperature is 35 ° C or higher in the summer is increasing, and concrete construction work is stopped or the construction time is changed, and hydraulic lime resistance. It may be necessary to take measures such as taking measures so that the temperature of the composition does not exceed 35 ° C.
そこで、本発明は上記実情に鑑み、３５℃以上の高温環境下であっても、２５℃未満の環境（標準環境）と同等のスランプ保持性、凝結時間、及びブリーディング率の発現等の効果を発揮し、水硬性組成物の良好な流動性を保持することの可能な、特に水硬性組成物を製造する際に各種原料とともに同時に添加される「同時添加型」の水硬性組成物用添加剤、及び当該水硬性組成物を添加した水硬性組成物の提供を課題とするものである。 Therefore, in view of the above circumstances, the present invention has effects such as slump retention, setting time, and bleeding rate equivalent to those in an environment of less than 25 ° C (standard environment) even in a high temperature environment of 35 ° C or higher. A "simultaneous addition type" additive for hydraulic composition that can be exerted and can maintain good fluidity of the hydraulic composition, in particular, is added simultaneously with various raw materials when producing the hydraulic composition. , And the provision of a hydraulic composition to which the hydraulic composition is added is an object.
本願出願人らは、上記課題を解決すべく鋭意検討を行った結果、下記に示すＡ成分、Ｂ成分、Ｃ成分、及びＤ成分を所定の配合比率で含有した水硬性組成物用添加剤を用いることが好適であることを見出した。本発明によれば、以下の水硬性組成物用添加剤、及び水硬性組成物が提供される。 As a result of diligent studies to solve the above problems, the applicants of the present application have obtained an additive for a hydraulic composition containing the following components A, B, C, and D in a predetermined blending ratio. It has been found that it is suitable to use. According to the present invention, the following additives for hydraulic composition and hydraulic composition are provided.
［１］ 下記のＡ成分と、下記のＢ成分と、下記のＣ成分と、下記のＤ成分とを含有する水硬性組成物用添加剤であって、前記Ａ成分、前記Ｂ成分、前記Ｃ成分、及び前記Ｄ成分の含有割合の合計を１００質量％とした場合において、前記Ａ成分を５〜６５質量％、前記Ｂ成分を１５〜７５質量％、前記Ｃ成分を１０〜７０質量％、及び前記Ｄ成分を１０〜７０質量％の割合でそれぞれ含有する水硬性組成物用添加剤。
Ａ成分：下記の化１で示される構成単位１及び下記の構成単位２を有し、
前記Ａ成分において構成単位１及び構成単位２の合計１００質量％に対し、前記構成単位１を７０〜９５質量％、及び前記構成単位２を５〜３０質量％の割合でそれぞれ含有し、前記Ａ成分中のカルボン酸及びその塩の酢酸換算含有割合が０．１〜４．０質量％であり、かつ、質量平均分子量が１０００〜２０００００であるビニル共重合体
構成単位１：
構成単位２：
（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成される構成単位
Ｂ成分：下記の化２で示される構成単位３及び下記の構成単位４を有し、
前記Ｂ成分において構成単位３及び構成単位４の合計１００質量％に対し、前記構成単位３を６５〜９５質量％、及び前記構成単位４を５〜３５質量％の割合でそれぞれ含有し、前記Ｂ成分中のカルボン酸及びその塩の酢酸換算含有割合が４．０質量％を超え４０．０質量％以下であり、かつ、質量平均分子量が１０００〜２０００００であるビニル共重合体
構成単位３：
構成単位４：
不飽和カルボン酸及びその塩から選ばれる少なくとも一つから形成される構成単位
Ｃ成分：オキシカルボン酸及びその塩から選ばれる少なくとも一つ
Ｄ成分：糖類
[1] An additive for a water-hard composition containing the following A component, the following B component, the following C component, and the following D component, the A component, the B component, and the C. When the total content of the components and the D component is 100% by mass, the A component is 5 to 65% by mass, the B component is 15 to 75% by mass, and the C component is 10 to 70% by mass. And an additive for a water-hard composition containing the D component in a proportion of 10 to 70% by mass, respectively.
Component A: It has the structural unit 1 shown in Chemical formula 1 below and the structural unit 2 below.
In the component A, the structural unit 1 is contained in an amount of 70 to 95% by mass and the structural unit 2 is contained in a proportion of 5 to 30% by mass with respect to a total of 100% by mass of the structural unit 1 and the structural unit 2. A vinyl copolymer having an acetic acid-equivalent content of carboxylic acid and its salt in the components of 0.1 to 4.0% by mass and a mass average molecular weight of 1000 to 200,000.
Structural unit 2:
A structural unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate. It has a structural unit 3 shown and a structural unit 4 below.
In the B component, the constituent unit 3 is contained in an amount of 65 to 95% by mass and the constituent unit 4 is contained in a proportion of 5 to 35% by mass with respect to a total of 100% by mass of the constituent unit 3 and the constituent unit 4, respectively. Vinyl copolymer constituent unit 3: The acetic acid-equivalent content ratio of the carboxylic acid and its salt in the components is more than 4.0% by mass and 40.0% by mass or less, and the mass average molecular weight is 1000 to 200,000.
Structural unit 4:
Constituent unit formed from at least one selected from unsaturated carboxylic acid and its salt C component: At least one selected from oxycarboxylic acid and its salt D component: Sugar
［２］ 前記Ａ成分は、下記の構成単位５、及び下記の構成単位６を更に有し、
前記Ａ成分中に前記構成単位５を０．１〜２０質量％、及び前記構成単位６を０〜１０質量％の割合でそれぞれ含有する前記［１］に記載の水硬性組成物用添加剤。
構成単位５：
不飽和カルボン酸及びその塩から選ばれる少なくとも一つから形成される構成単位
構成単位６：
分子中にビニル基を有する単量体から形成される構成単位
[2] The component A further has the following structural unit 5 and the following structural unit 6.
The additive for a hydraulic composition according to the above [1], wherein the constituent unit 5 is contained in the component A in an amount of 0.1 to 20% by mass and the constituent unit 6 is contained in a proportion of 0 to 10% by mass.
Constituent unit 5:
Constituent units formed from at least one selected from unsaturated carboxylic acids and salts thereof Constituent units 6:
A building block formed from a monomer having a vinyl group in the molecule
［３］ 前記Ｂ成分は、下記の構成単位７、及び下記の構成単位８を更に有し、
前記Ｂ成分中に前記構成単位７を０〜５質量％、及び前記構成単位８を０〜１０質量％の割合でそれぞれ含有する前記［１］または［２］に記載の水硬性組成物用添加剤。
構成単位７：
（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成される構成単位
構成単位８：
分子中にビニル基を有する単量体から形成される構成単位
[3] The B component further has the following structural unit 7 and the following structural unit 8.
The addition for a hydraulic composition according to the above [1] or [2], wherein the constituent unit 7 is contained in the component B in an amount of 0 to 5% by mass and the constituent unit 8 is contained in a proportion of 0 to 10% by mass, respectively. Agent.
Structural unit 7:
Constituent unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate Constituent unit 8:
A building block formed from a monomer having a vinyl group in the molecule
［４］ 前記Ａ成分を５〜５０質量％、前記Ｂ成分を１５〜６０質量％、前記Ｃ成分を１０〜５０質量％、及び前記Ｄ成分を１０〜５０質量％の割合でそれぞれ含有する前記［１］〜［３］のいずれかに記載の水硬性組成物用添加剤。 [4] The component A is contained in an amount of 5 to 50% by mass, the component B is contained in an amount of 15 to 60% by mass, the component C is contained in an amount of 10 to 50% by mass, and the component D is contained in an amount of 10 to 50% by mass. The additive for a water-hard composition according to any one of [1] to [3].
［５］ 前記Ｃ成分は、グルコン酸及びグルコン酸ナトリウム塩から選ばれる少なくとも一つである前記［１］〜［４］のいずれかに記載の水硬性組成物用添加剤。 [5] The additive for a hydraulic composition according to any one of the above [1] to [4], wherein the C component is at least one selected from gluconic acid and sodium gluconate salt.
［６］ 前記Ｄ成分は、スクロースである前記［１］〜［５］のいずれかに記載の水硬性組成物用添加剤。 [6] The additive for a hydraulic composition according to any one of the above [1] to [5], wherein the D component is sucrose.
［７］ 下記の（１）〜（３）から選ばれる少なくとも一つの使用条件下で使用される前記［１］〜［６］のいずれかに記載の水硬性組成物用添加剤。
（１）型枠への水硬性組成物の打ち込み時の水硬性組成物温度が２５℃以上
（２）型枠への水硬性組成物の打ち込み時の日平均気温が２５℃以上
（３）型枠への水硬性組成物の打ち込み日の最高気温が３０℃以上
[7] The additive for a hydraulic composition according to any one of the above [1] to [6], which is used under at least one use condition selected from the following (1) to (3).
(1) The water-hard composition temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (2) The daily average temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (3) type The maximum temperature on the day when the water-hard composition is driven into the frame is 30 ° C or higher.
［８］ 前記［１］〜［７］のいずれかに記載の水硬性組成物用添加剤と、セメントを含有する結合材と、水と、細骨材と、粗骨材とを含有する水硬性組成物。 [8] Water containing the additive for hydraulic composition according to any one of [1] to [7], a binder containing cement, water, fine aggregate, and coarse aggregate. Hard composition.
本発明の水硬性組成物用添加剤によれば、特に水硬性組成物の製造時に各種原料と同時に添加することにより、高温環境下であっても標準期と同等のスランプ保持性等を発揮可能な水硬性組成物を製造することができる。これにより、高温環境下であっても標準環境と同等の作業により、施工不良等のない安定したコンクリート等の水硬性組成物を得ることができる。 According to the additive for hydraulic composition of the present invention, it is possible to exhibit slump retention equivalent to that in the standard period even in a high temperature environment by adding it at the same time as various raw materials, particularly when producing a hydraulic composition. A hydraulic composition can be produced. As a result, a stable hydraulic composition such as concrete without construction defects can be obtained by the same work as in a standard environment even in a high temperature environment.
以下、本発明の水硬性組成物用添加剤、及び水硬性組成物の実施の形態について説明する。なお、本発明の水硬性組成物用添加剤、及び水硬性組成物は、以下の実施形態に限定されるものではなく、本発明の範囲を逸脱しない限りにおいて、種々の設計の変更、修正、改良等を加え得るものである。なお、以下の実施例等において、特に記載しない限り、％は質量％を、または部は質量部を意味するものとする。 Hereinafter, the additive for the hydraulic composition of the present invention and the embodiment of the hydraulic composition will be described. The additive for the hydraulic composition of the present invention and the hydraulic composition are not limited to the following embodiments, and various design changes, modifications, and modifications are made as long as they do not deviate from the scope of the present invention. Improvements and the like can be added. In the following examples and the like, unless otherwise specified,% means mass%, or parts means parts by mass.
本発明の一実施形態の水硬性組成物用添加剤は、Ａ成分と、Ｂ成分と、Ｃ成分と、Ｄ成分とを含有するものである。 The additive for a hydraulic composition according to an embodiment of the present invention contains a component A, a component B, a component C, and a component D.
本実施形態の水硬性組成物用添加剤に供するＡ成分は、分子中に構成単位１及び構成単位２を有するビニル共重合体として構成されるものであり、一方、Ｂ成分は分子中に構成単位３及び構成単位４を有するビニル共重合体として構成されるものであり、Ｃ成分はオキシカルボン酸及びその塩から選ばれる少なくとも一つからなるものであり、及び、Ｄ成分は糖類である。 The component A provided for the additive for the water-hard composition of the present embodiment is composed of a vinyl copolymer having a constituent unit 1 and a constituent unit 2 in the molecule, while the component B is composed in the molecule. It is configured as a vinyl copolymer having a unit 3 and a constituent unit 4, the C component is composed of at least one selected from oxycarboxylic acid and a salt thereof, and the D component is a saccharide.
Ａ成分に含まれる構成単位１は、下記の化１で示されるものである。 The structural unit 1 contained in the component A is as shown in Chemical formula 1 below.
ここで、化１において、Ｒ１は炭素数２〜５のアルケニル基、または炭素数３〜４の不飽和アシル基であり、Ａ１Ｏは炭素数２〜４のオキシアルキレン基であり、ｍは２〜３００の整数であり、Ｒ２は水素原子、炭素数１〜２２のアルキル基、または炭素数１〜２２の脂肪族アシル基をそれぞれ示している。 Here, in Chemical formula 1 , R 1 is an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 to 4 carbon atoms, and A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. Is an integer of 2 to 300, and R 2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aliphatic acyl group having 1 to 22 carbon atoms, respectively.
上記に既定される化１の化合物としては、例えば、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−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−メトキシ−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ポリオキシプロピレン、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−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−ブトキシ−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ポリオキシプロピレン、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−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−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−メトキシ−ポリオキシエチレンポリオキシプロピレン、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−ブトキシ−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−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−メトキシ−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ポリオキシプロピレン、α−メタクリロイル−ω−ブトキシ−ポリオキシエチレン、α−メタクリロイル−ω−ブトキシ−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。 Examples of the compound of Formulation 1 defined above include α-allyl-ω-hydroxy-polyoxyethylene, α-allyl-ω-hydroxy-polyoxyethylene polyoxypropylene, and α-metharyl-ω-hydroxy-poly. Oxyethylene, α-Metalyl-ω-hydroxy-polyoxyethylene polyoxypropylene, α-Metalyl-ω-methoxy-polyoxyethylene, α-Metalyl-ω-methoxy-polyoxyethylene polyoxypropylene, α- (3-) Methyl-3-butenyl) -ω-hydroxy-polyoxyethylene, α- (3-methyl-3-butenyl) -ω-hydroxy-polyoxyethylene polyoxypropylene, α- (3-methyl-3-butenyl)- ω-butoxy-polyoxyethylene, α- (3-methyl-3-butenyl) -ω-butoxy-polyoxyethylene polyoxypropylene, α-acryloyl-ω-hydroxy-polyoxyethylene, α-acryloyl-ω-hydroxy -Polyoxyethylene polyoxypropylene, α-acryloyl-ω-methoxy-polyoxyethylene, α-acryloyl-ω-methoxy-polyoxyethylene polyoxypropylene, α-acryloyl-ω-butoxy-polyoxyethylene, α-acryloyl -Ω-Butoxy-Polyoxyethylene polyoxypropylene, α-methacryloyl-ω-hydroxy-polyoxyethylene, α-methacryloyl-ω-hydroxy-polyoxyethylene polyoxypropylene, α-methacryloyl-ω-methoxy-polyoxyethylene , Α-methacryloyl-ω-methoxy-polyoxyethylene polyoxypropylene, α-methacryloyl-ω-butoxy-polyoxyethylene, α-methacryloyl-ω-butoxy-polyoxyethylene polyoxypropylene and the like.
構成単位２は、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成される構成単位である。 The structural unit 2 is a structural unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate.
本実施形態の水硬性組成物用添加剤に供するＡ成分であるビニル共重合体は、更に分子中に構成単位５を有し、構成単位６を含んでいるものであっても構わない。ここで、構成単位５は、不飽和カルボン酸及びその塩から選ばれる少なくとも一つから形成される構成単位であり、構成単位６は分子中にビニル基を有する単量体から形成される構成単位である。 The vinyl copolymer which is the component A provided for the additive for the hydraulic composition of the present embodiment may further have a constituent unit 5 in the molecule and may contain the constituent unit 6. Here, the structural unit 5 is a structural unit formed from at least one selected from an unsaturated carboxylic acid and a salt thereof, and the structural unit 6 is a structural unit formed from a monomer having a vinyl group in the molecule. Is.
構成単位５は、不飽和カルボン酸及び／またはその塩から構成されるものであり、例えば、メタクリル酸、アクリル酸、及びマレイン酸等、或いはこれらの塩から選ばれる少なくとも一つから形成される構成単位を含むものである。塩としては、特に制限するものではないが、例えば、ナトリウム塩、カリウム塩などのアルカリ金属塩、カルシウム塩、マグネシウム塩など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、トリエタノールアミン塩等のアミン塩などが挙げられる。なかでもナトリウム塩とカルシウム塩が好ましい。一方、構成単位６は、例えば、（メタ）アリルスルホン酸及びその塩、アクリル酸ブチル、アクリルアミド、アクリロニトリル、ポリアルキレンイミン等から形成される構成単位を含むものである。 The structural unit 5 is composed of an unsaturated carboxylic acid and / or a salt thereof, and is formed of, for example, methacrylic acid, acrylic acid, maleic acid, or the like, or at least one selected from these salts. It includes units. The salt is not particularly limited, but for example, alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, diethanolamine salt, triethanolamine salt and the like. Examples include amine salts. Of these, sodium salts and calcium salts are preferable. On the other hand, the structural unit 6 includes, for example, a structural unit formed of (meth) allylsulfonic acid and a salt thereof, butyl acrylate, acrylamide, acrylonitrile, polyalkyleneimine and the like.
本実施形態の水硬性組成物用添加剤に供するＡ成分において、構成単位１及び構成単位２の合計１００質量％に対し、構成単位１を７０〜９５質量％及び構成単位２を５〜３０質量％含むものであり、構成単位１を７０〜９０質量％、及び構成単位２を１０〜３０質量％の割合で含むものが好ましく、構成単位１を７５〜８５質量％、及び構成単位２を１５〜２５質量％の割合で含むことが更に好ましい。 In the component A to be used as the additive for the water-hard composition of the present embodiment, the constituent unit 1 is 70 to 95% by mass and the constituent unit 2 is 5 to 30 mass% with respect to the total of 100% by mass of the constituent unit 1 and the constituent unit 2. %, The structural unit 1 is preferably 70 to 90% by mass, and the structural unit 2 is preferably 10 to 30% by mass, the structural unit 1 is 75 to 85% by mass, and the structural unit 2 is 15. It is more preferably contained in a proportion of ~ 25% by mass.
なお、Ａ成分において、上記の構成単位５及び構成単位６を含む場合において、構成単位１、構成単位２、構成単位５及び構成単位６の合計１００質量％に対し、構成単位５を０．１〜２０質量％の割合で、及び構成単位６を０〜１０質量％の割合でそれぞれ含むものであっても構わない。 When the component A includes the above-mentioned constitutional unit 5 and the constitutional unit 6, the constitutional unit 5 is 0.1 with respect to the total 100% by mass of the constitutional unit 1, the constitutional unit 2, the constitutional unit 5 and the constitutional unit 6. It may be contained in a ratio of about 20% by mass and the constituent unit 6 in a ratio of 0 to 10% by mass, respectively.
更に水硬性組成物添加剤に供するＡ成分のカルボン酸及びその塩の酢酸換算含有割合は、０．１〜４．０質量％に範囲内に規定され、０．１〜３．０質量％であることが好ましく、０．１〜２．０質量％であることがより好ましい。本発明において、酢酸換算含有割合は、本発明の水硬性組成物用添加剤に含まれるＡ成分に含まれるカルボン酸及びその塩のカルボキシル基及びその塩を電位差測定して酢酸に換算したときの質量％であり、具体的にはＡ成分の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ｐＨ＝２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Ａ成分の質量に対する割合を算出した値（質量％）である。 Further, the acetic acid-equivalent content ratio of the carboxylic acid of component A and its salt to be used as the additive for the water-hard composition is defined in the range of 0.1 to 4.0% by mass, and is 0.1 to 3.0% by mass. It is preferably 0.1 to 2.0% by mass, and more preferably 0.1 to 2.0% by mass. In the present invention, the acetic acid conversion content ratio is obtained when the carboxyl group of the carboxylic acid and its salt contained in the component A contained in the additive for the water-hard composition of the present invention and the salt thereof are measured at an equivalence point and converted into acetic acid. It is mass%. Specifically, a 40 mass% aqueous solution of component A was diluted 20-fold with ion-exchanged water and a hydrochloric acid aqueous solution was added to adjust the pH to 2, and the solution was subjected to a potential differential titration device. Was titrated with an aqueous potassium hydroxide solution having a concentration of 0.1 mol / L, and the mass of acetic acid in the same molar amount as potassium hydroxide consumed between the first equivalence point and the second equivalence point was determined. It is a value (mass%) calculated as a ratio of the mass of hydrochloric acid to the mass of the original component A.
本実施形態の水硬性組成物用添加剤に供するＡ成分の質量平均分子量は、ゲルパーミエーションクロマトグラフィーで測定することができ、好ましくはプルラン換算で１０００〜２０００００であり、より好ましくは５０００〜２０００００であり、更に好ましくは８０００〜１０００００である。 The mass average molecular weight of the component A used in the additive for the water-hard composition of the present embodiment can be measured by gel permeation chromatography, preferably 1000 to 200,000 in terms of pullulan, and more preferably 5000 to 20000. It is more preferably 8000 to 100,000.
このようなＡ成分は、公知のラジカル重合反応により得ることができる。これには、溶媒に水を使用したラジカル重合、溶媒に有機溶媒を使用したラジカル重合、無溶媒のラジカル重合による方法が挙げられる。ラジカル重合における反応温度は、好ましくは０〜１２０℃であり、より好ましくは２０〜１００℃であり、更に好ましくは５０〜９０℃である。ラジカル重合に使用す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、２，２´−アゾビス（２−アミジノプロパン）二塩酸塩、２，２´−アゾビス（イソブチロニトリル）等のアゾ系化合物が挙げられ、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。これらは、亜硫酸塩やＬ−アスコルビン酸等の還元性物質、更にはアミン等と組み合わせ、レドックス開始剤として使用することもできる。得られるＡ成分の質量平均分子量を所望の範囲とするため、２−メルカプトエタノール、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオグリコール酸、チオグリセリン、チオリンゴ酸等の連鎖移動剤を使用することもできる。これらのラジカル重合開始剤や還元性物質、連鎖移動剤は、それぞれ単独で使用しても２種類以上を併用してもよい。本実施形態の水硬性組成物用添加剤に供するＡ成分は、水や有機溶媒を含んだまま使用してもよく、乾燥させて粉末として使用してもよく、水や有機溶媒を含んだままで無機多孔質粉体に担持させて使用してもよく、水や有機溶媒を含んだままで無機多孔質粉体に担持させ、かつ乾燥させて使用してもよい。反応系内の圧力は特に限定されないが、大気圧が好ましい。 Such a component A can be obtained by a known radical polymerization reaction. Examples of this include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and radical polymerization without a solvent. The reaction temperature in radical polymerization is preferably 0 to 120 ° C, more preferably 20 to 100 ° C, and even more preferably 50 to 90 ° C. The radical polymerization initiator used for radical polymerization is a peroxide such as hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2, Examples thereof include azo compounds such as 2'-azobis (isobutyronitrile), and the type is not particularly limited as long as it decomposes at the polymerization reaction temperature and generates radicals. These can also be used as a redox initiator in combination with reducing substances such as sulfites and L-ascorbic acid, as well as amines and the like. Chain transfer agents such as 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid, thioglycerin, and thioapple acid are used in order to set the mass average molecular weight of the obtained component A in a desired range. You can also do it. These radical polymerization initiators, reducing substances, and chain transfer agents may be used alone or in combination of two or more. The component A to be used as the additive for the water-hard composition of the present embodiment may be used while containing water or an organic solvent, may be dried and used as a powder, or may be used as a powder while containing water or an organic solvent. It may be used by supporting it on an inorganic porous powder, or it may be used by supporting it on an inorganic porous powder while containing water or an organic solvent and then drying it. The pressure in the reaction system is not particularly limited, but atmospheric pressure is preferable.
本実施形態の水硬性組成物用添加剤に供するＢ成分に含まれる構成単位３は、下記の化２で示されるものである。 The structural unit 3 contained in the component B provided for the additive for the hydraulic composition of the present embodiment is as shown in Chemical formula 2 below.
ここで、化２において、Ｒ３は炭素数２〜５のアルケニル基、または炭素数３〜４の不飽和アシル基であり、Ａ２Ｏは炭素数２〜４のオキシアルキレン基であり、ｎは２〜３００の整数であり、Ｒ４は水素原子、炭素数１〜２２のアルキル基、または炭素数１〜２２の脂肪族アシル基をそれぞれ示している。 Here, in Chemical formula 2, R 3 is an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 to 4 carbon atoms, and A 2 O is an oxyalkylene group having 2 to 4 carbon atoms. Is an integer of 2 to 300, and R 4 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aliphatic acyl group having 1 to 22 carbon atoms, respectively.
上記に既定される化２の化合物としては、例えば、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−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−メトキシ−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ポリオキシプロピレン、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−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−ブトキシ−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ポリオキシプロピレン、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−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−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−メトキシ−ポリオキシエチレンポリオキシプロピレン、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−ブトキシ−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−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−メトキシ−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ポリオキシプロピレン、α−メタクリロイル−ω−ブトキシ−ポリオキシエチレン、α−メタクリロイル−ω−ブトキシ−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。 Examples of the compound of Chemical formula 2 defined above include α-allyl-ω-hydroxy-polyoxyethylene, α-allyl-ω-hydroxy-polyoxyethylene polyoxypropylene, and α-metharyl-ω-hydroxy-poly. Oxyethylene, α-Metalyl-ω-hydroxy-polyoxyethylene polyoxypropylene, α-Metalyl-ω-methoxy-polyoxyethylene, α-Metalyl-ω-methoxy-polyoxyethylene polyoxypropylene, α- (3-) Methyl-3-butenyl) -ω-hydroxy-polyoxyethylene, α- (3-methyl-3-butenyl) -ω-hydroxy-polyoxyethylene polyoxypropylene, α- (3-methyl-3-butenyl)- ω-butoxy-polyoxyethylene, α- (3-methyl-3-butenyl) -ω-butoxy-polyoxyethylene polyoxypropylene, α-acryloyl-ω-hydroxy-polyoxyethylene, α-acryloyl-ω-hydroxy -Polyoxyethylene polyoxypropylene, α-acryloyl-ω-methoxy-polyoxyethylene, α-acryloyl-ω-methoxy-polyoxyethylene polyoxypropylene, α-acryloyl-ω-butoxy-polyoxyethylene, α-acryloyl -Ω-Butoxy-Polyoxyethylene polyoxypropylene, α-methacryloyl-ω-hydroxy-polyoxyethylene, α-methacryloyl-ω-hydroxy-polyoxyethylene polyoxypropylene, α-methacryloyl-ω-methoxy-polyoxyethylene , Α-methacryloyl-ω-methoxy-polyoxyethylene polyoxypropylene, α-methacryloyl-ω-butoxy-polyoxyethylene, α-methacryloyl-ω-butoxy-polyoxyethylene polyoxypropylene and the like.
本実施形態の水硬性組成物用添加剤に供するＢ成分に含まれる構成単位４は、不飽和カルボン酸及び／またはその塩から選ばれる少なくとも一つから形成された構成単位である。構成単位４は、既に説明したＡ成分における構成単位５として示したものと同一構成の中から選ぶことが可能であり、ここでは詳細な説明は省略する。 The structural unit 4 contained in the component B provided for the additive for the water-hard composition of the present embodiment is a structural unit formed from at least one selected from unsaturated carboxylic acids and / or salts thereof. The structural unit 4 can be selected from the same configurations as those shown as the structural unit 5 in the component A already described, and detailed description thereof will be omitted here.
本実施形態の水硬性組成物用添加剤に供するＢ成分であるビニル共重合体は、更に分子中に、任意の構成単位として、構成単位７、及び構成単位８を含んでいてもよい。 The vinyl copolymer, which is a component B to be used as the additive for the hydraulic composition of the present embodiment, may further contain a structural unit 7 and a structural unit 8 as arbitrary structural units in the molecule.
構成単位７は、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成された構成単位を含むものである。構成単位７は、既に説明したＡ成分における構成単位２として示したものと同一構成の中から選ぶことが可能である。 The structural unit 7 includes a structural unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate. .. The structural unit 7 can be selected from the same configurations as those shown as the structural unit 2 in the component A already described.
構成単位８は、（メタ）アリルスルホン酸及びその塩、アクリル酸ブチル、アクリルアミド、アクリロニトリル、ポリアルキレンイミン等から形成される構成単位を含むものであり、既に説明したＡ成分における構成単位６として示したものと同一構成の中から選ぶことが可能である。 The structural unit 8 contains a structural unit formed of (meth) allylsulfonic acid and a salt thereof, butyl acrylate, acrylamide, acrylonitrile, polyalkyleneimine, etc., and is shown as the structural unit 6 in the component A already described. It is possible to choose from the same configuration as the one.
本実施形態の水硬性組成物用添加剤に供するＢ成分において、構成単位３及び構成単位４の合計１００質量％に対し、構成単位３を６５〜９５質量％及び構成単位４を５〜３５質量％含むものであり、構成単位３を７０〜９５質量％、及び構成単位４を５〜３０質量％の割合で含むものが好ましく、構成単位３を７５〜９０質量％、及び構成単位４を１０〜２５質量％の割合で含むことが更に好ましい。 In the component B to be used as the additive for the water-hard composition of the present embodiment, the constituent unit 3 is 65 to 95% by mass and the constituent unit 4 is 5 to 35% by mass with respect to the total of 100% by mass of the constituent unit 3 and the constituent unit 4. %, The structural unit 3 is preferably 70 to 95% by mass, and the structural unit 4 is preferably 5 to 30% by mass, the structural unit 3 is 75 to 90% by mass, and the structural unit 4 is 10. It is more preferably contained in a proportion of ~ 25% by mass.
Ｂ成分において、構成単位７及び構成単位８を含む場合においては、構成単位の合計１００質量％に対して、構成単位７を０〜５質量％の割合で、及び、構成単位８を０〜１０質量％の割合でそれぞれ含むものであっても構わない。 When the constituent unit 7 and the constituent unit 8 are included in the B component, the constituent unit 7 is 0 to 5% by mass and the constituent unit 8 is 0 to 10 with respect to the total 100% by mass of the constituent units. It may be contained in a proportion of% by mass.
本実施形態の水硬性組成物用混和剤に供するＢ成分中のカルボン酸及びその塩の酢酸換算含有割合は４．０質量％を超え４０．０質量％以下であり、４．０質量％を超え３０．０質量％以下であることが好ましく、４．０質量％を超え２０．０質量％以下であることがより好ましい。なお、Ｂ成分中の酢酸換算含有割合は、本発明の水硬性組成物用添加剤に含まれるＢ成分に含まれるカルボン酸及びその塩のカルボキシル基及びその塩を電位差測定して酢酸に換算したときの質量％であり、上記のＡ成分の酢酸換算含有割合の算出と同一であるため、ここでは説明を省略する。 The acetic acid-equivalent content ratio of the carboxylic acid and its salt in the component B to be used in the admixture for the water-hard composition of the present embodiment is more than 4.0% by mass and 40.0% by mass or less, and 4.0% by mass. It is preferably more than 30.0% by mass or less, and more preferably more than 4.0% by mass and 20.0% by mass or less. The acetic acid equivalent content ratio in the B component was converted to acetic acid by measuring the potential difference of the carboxyl group of the carboxylic acid and its salt contained in the B component contained in the additive for the water-hard composition of the present invention and its salt. Since it is the mass% of the above and is the same as the calculation of the acetic acid conversion content ratio of the component A described above, the description thereof will be omitted here.
本実施形態の水硬性組成物用混和剤に供するＢ成分の質量平均分子量は、ゲルパーミエーションクロマトグラフィーで測定することができ、好ましくはプルラン換算で１０００〜２０００００であり、より好ましくは５０００〜２０００００であり、更に好ましくは８０００〜１０００００である。 The mass average molecular weight of the component B to be used in the admixture for the hydraulic composition of the present embodiment can be measured by gel permeation chromatography, preferably 1000 to 200,000 in terms of pullulan, and more preferably 5000 to 20000. It is more preferably 8000 to 100,000.
このようなＢ成分は、上述したＡ成分と同様、ラジカル重合反応により得ることができる。 Such a component B can be obtained by a radical polymerization reaction like the component A described above.
本実施形態の水硬性組成物用添加剤は、Ａ成分、Ｂ成分、Ｃ成分、及びＤ成分の合計を１００質量％とした場合において、Ａ成分を５〜６５質量％、Ｂ成分を１５〜７５質量％、Ｃ成分を１０〜７０質量％、及びＤ成分を１０〜７０質量％の割合で含有することを特徴とするものであり、Ａ成分を５〜５０質量％、Ｂ成分を１５〜６０質量％、Ｃ成分を１０〜５０質量％、及びＤ成分を１０〜５０質量％の割合で含有するものが好ましく、Ａ成分を１０〜２０質量％、Ｂ成分を２０〜５０質量％、Ｃ成分を１５〜４０質量％、及びＤ成分を１５〜４０質量％の割合で含有するものが更に好ましい。 The additive for a water-hard composition of the present embodiment has 5 to 65% by mass of A component and 15 to 65% by mass of B component when the total of A component, B component, C component and D component is 100% by mass. It is characterized by containing 75% by mass of 75% by mass, 10 to 70% by mass of C component, and 10 to 70% by mass of D component, 5 to 50% by mass of A component, and 15 to 50% by mass of B component. It is preferable that 60% by mass, C component is 10 to 50% by mass, and D component is 10 to 50% by mass, A component is 10 to 20% by mass, B component is 20 to 50% by mass, and C. It is more preferable that the component is contained in an proportion of 15 to 40% by mass and the component D is contained in a proportion of 15 to 40% by mass.
本実施形態の水硬性組成物用添加剤に供するＣ成分におけるオキシカルボン酸及び／またはその塩としてグルコン酸、グリコール酸、グリセリン酸、酒石酸、クエン酸、リンゴ酸、グルコヘプトン酸、アラボン酸等や、それらの塩が挙げられる。なかでもグルコン酸及びグルコン酸ナトリウム塩から選ばれる少なくとも一つを用いるものが好適である。更に、Ｄ成分における糖類としては、単糖類、二糖類、少糖類（オリゴ糖類）、多糖類及び糖アルコールが挙げられる。単糖類としては、リボース、アラビノース、キシロース、リキソース、リブロース、キシルロース、アピオース等の五炭糖、アロース、アルトロース、グルコース、マンノース、グロース、イドース、ガラクトース、タロース、プシコース、フルクトース、ソルボース、タガトース等の六炭糖、セドヘプツロース、コリオース等の七炭糖等が挙げられる。二糖類としては、スクロース、ラクツロース、ラクトース、マルトース、トレハロース、セロビオース、コージビオース、ニゲロース、イソマルトース、イソトレハロース、ソホロース、ラミナリビオース、ゲンチオビオース、ツラノース、パラチノース、メリビオース、キシロビオース等が挙げられる。少糖類（オリゴ糖類）としては、ラフィノース、マルトトリオース、メレジトース等の三糖類、スタキオース等の四糖類、イソマルトオリゴ糖、フルクトオリゴ糖、ガラクトオリゴ糖、キトサンオリゴ糖、ゲンチオオリゴ糖等のオリゴ糖が挙げられる。多糖類としては、デンプン、アミロース、アミロペクチン、グリコーゲン、セルロース、キチン、アガロース、カラギーナン、ヘパリン、グルコマンナン、シクロデキストリン等が挙げられる。これらの多糖類は、単糖、二糖、少糖類を含んでいてよい。糖アルコールとしては、エリトリトール、アラビトール、キシリトール、ガラクチトール、ソルビトール、マンニトール等が挙げられる。なかでもスクロースを用いるものが好適である。 Gluconic acid, glycolic acid, glyceric acid, tartaric acid, citric acid, malic acid, glucoheptonic acid, alabonic acid, etc. These salts are mentioned. Among them, those using at least one selected from gluconic acid and sodium gluconate salt are preferable. Further, examples of the saccharide in the D component include monosaccharides, disaccharides, oligosaccharides (oligosaccharides), polysaccharides and sugar alcohols. Examples of monosaccharides include ribose, arabinose, xylose, lyxose, ribulose, xylulose, apiose and other pentacarbon sugars, allose, altrose, glucose, mannose, gulose, idose, galactose, tarose, psicose, fructose, sorbose, tagatose and the like. Examples include six-carbon sugar, sedoheptulose, seven-carbon sugar such as coriose, and the like. Examples of the disaccharide include sucrose, lactose, lactose, maltose, trehalose, cellobiose, kojibiose, nigerose, isomaltose, isotrehalose, sophorose, laminaribiose, gentiobiose, turanose, palatinose, melibiose, xylobiose and the like. Examples of oligosaccharides include trisaccharides such as raffinose, maltotriose and melezitose, tetrasaccharides such as stachyose, oligosaccharides such as isomaltooligosaccharide, fructo-oligosaccharide, galactooligosaccharide, chitosan oligosaccharide and gentio-oligosaccharide. .. Examples of the polysaccharide include starch, amylose, amylopectin, glycogen, cellulose, chitin, agarose, carrageenan, heparin, glucomannan, cyclodextrin and the like. These polysaccharides may include monosaccharides, disaccharides and oligosaccharides. Examples of sugar alcohols include erythritol, arabitol, xylitol, galactitol, sorbitol, mannitol and the like. Of these, those using sucrose are preferable.
本実施形態の水硬性組成物用添加剤は、下記の（１）〜（３）から選ばれる少なくとも一つの使用条件下で特に好適に使用することができる。
（１）型枠への水硬性組成物の打ち込み時の水硬性組成物温度が２５℃以上
（２）型枠への水硬性組成物の打ち込み時の日平均気温が２５℃以上
（３）型枠への水硬性組成物の打ち込み日の最高気温が３０℃以上
すなわち、上述した標準環境から逸脱した高温環境下での使用に好適に使用することができる。
The additive for a hydraulic composition of the present embodiment can be particularly preferably used under at least one use condition selected from the following (1) to (3).
(1) The water-hard composition temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (2) The daily average temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (3) type The maximum temperature on the day when the water-hard composition is driven into the frame is 30 ° C. or higher, that is, it can be suitably used in a high temperature environment deviating from the above-mentioned standard environment.
本実施形態の水硬性組成物は以上説明したような本実施形態の水硬性組成物用添加剤を使用して調製したものであり、セメントペースト、モルタル、コンクリート等のセメント組成物であることが好ましい。セメント組成物は、結合材として、少なくともセメントを使用したものであるが、セメントを単独で使用してもよく、また、セメントと微粉末混和材料を併用してもよい。このようなセメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、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、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が挙げられる。また、微粉末混和材料としては、高炉スラグ微粉末、シリカフューム、フライアッシュ、石灰石微粉末、石粉、膨張材等が挙げられる。 The hydraulic composition of the present embodiment is prepared by using the additive for the hydraulic composition of the present embodiment as described above, and may be a cement composition such as cement paste, mortar, or concrete. preferable. The cement composition uses at least cement as a binder, but cement may be used alone, or cement and a fine powder admixture may be used in combination. Examples of such cement include various Portland cements such as ordinary Portland cement, early-strength Portland cement, moderate heat Portland cement, and low heat Portland cement, and various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement. Examples of the fine powder admixture include blast furnace slag fine powder, silica fume, fly ash, limestone fine powder, stone powder, and expansion material.
更に、本実施形態の水硬性組成物は、水と骨材を含むことも好ましい。骨材としては、細骨材や粗骨材などの任意の適切な骨材を採用し得る。このような骨材のうち、細骨材としては、川砂、山砂、陸砂、珪砂、砕砂、高炉スラグ細骨材などが挙げられ、粗骨材としては、川砂利、山砂利、陸砂利、砕石、高炉スラグ粗骨材などが挙げられる。 Further, the hydraulic composition of the present embodiment preferably contains water and an aggregate. As the aggregate, any suitable aggregate such as fine aggregate or coarse aggregate can be adopted. Among such aggregates, fine aggregates include river sand, mountain sand, land sand, silica sand, crushed sand, blast furnace slag fine aggregate, and coarse aggregates include river gravel, mountain gravel, and land gravel. , Crushed stone, blast furnace slag coarse aggregate, etc.
更に、本実施形態の水硬性組成物においては、水結合材比が３０〜７０％であるのが好ましく、４０〜６５％であるのがより好ましい。なお、水結合材比とは、水硬性組成物中のセメントなどの結合材１００質量部に対する水の質量部の比であり、水が５０質量部となる場合は水結合材比が５０％となる。 Further, in the hydraulic composition of the present embodiment, the water binder ratio is preferably 30 to 70%, more preferably 40 to 65%. The water binder ratio is the ratio of the mass part of water to 100 parts by mass of the binder such as cement in the hydraulic composition, and when the water is 50 parts by mass, the water binder ratio is 50%. Become.
更に、本実施形態の水硬性組成物は、効果が損なわれない範囲内で、適宜、減水剤、ＡＥ減水剤、高性能ＡＥ減水剤、ＡＥ調整剤、消泡剤、凝結遅延剤、硬化促進剤、収縮低減剤、防腐剤、防水剤、防錆剤等を含有させることができる。 Further, the water-hardening composition of the present embodiment appropriately contains a water-reducing agent, an AE water-reducing agent, a high-performance AE water-reducing agent, an AE adjusting agent, a defoaming agent, a setting retarder, and a hardening accelerator, as long as the effect is not impaired. It can contain agents, shrinkage reducing agents, preservatives, waterproofing agents, rust preventives and the like.
以下、本発明の水硬性組成物用添加剤、及び水硬性組成物による効果を明確にするために、下記に示す実施例に基づいて説明を行う。しかしながら、本発明の水硬性組成物用添加剤、及び水硬性組成物は、かかる実施例に限定されるものではない。また、以下に示す実施例及び比較例において、特に断りのない限り、「部」は質量部を示し、「％」は質量％を意味するものとする。 Hereinafter, in order to clarify the effects of the additive for the hydraulic composition of the present invention and the hydraulic composition, the description will be given based on the examples shown below. However, the additive for hydraulic composition and the hydraulic composition of the present invention are not limited to such examples. Further, in the examples and comparative examples shown below, unless otherwise specified, "parts" means parts by mass and "%" means mass%.
（１）Ａ成分（ビニル共重合体の合成）
水硬性組成物用添加剤に供されるＡ成分として、下記表１に示す構成単位１及び構成単位２と、構成単位５及び構成単位６によって構成されたビニル共重合体からなる３種類（ＰＣ−１，ＰＣ−２，ＰＣ−３）を用いた。ここで、ＰＣ−１，ＰＣ−２，ＰＣ−３は、それぞれ各構成単位１，２，５，６の種類及び配合比率がそれぞれ異なるものである。
(1) Component A (Synthesis of vinyl copolymer)
As the component A used in the additive for the water-hard composition, there are three types (PC) composed of the structural unit 1 and the structural unit 2 shown in Table 1 below, and the vinyl copolymer composed of the structural unit 5 and the structural unit 6. -1, PC-2, PC-3) were used. Here, PC-1, PC-2, and PC-3 have different types and blending ratios of the constituent units 1, 2, 5, and 6, respectively.
（１−１）製造例１［ビニル共重合体（ＰＣ−１の合成）］
イオン交換水７８．０ｇを温度計、撹拌機、窒素導入管を備えた反応容器（以下、同様の反応容器を使用）に仕込み、撹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℃に保持した。次に、イオン交換水１４１．７ｇ、α−メタクリロイル−ω−メトキシ−ポリ（９モル）オキシエチレン１４７．８ｇ、アクリル酸ヒドロキシエチル４５．３ｇ、メタクリル酸３．９ｇ、及び連鎖移動剤として２−メルカプトエタノール１．４ｇ（分子量 ７８．１）を均一に溶解させた水溶液を２時間かけて滴下するとともに、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ｐＨ＝６に調整し、イオン交換水にて濃度を４０％に調整して、ビニル共重合体（ＰＣ−１）の４０％水溶液を得た。このビニル共重合体（ＰＣ−１）をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量は４１０００であった。なお、ビニル共重合体（ＰＣ−３）は、上記製造例１の合成方法に準拠し、構成単位１、構成単位２、及び構成単位５として使用する化合物及び配合割合を変化させ、連鎖移動剤として３−メルカプトプロピオン酸を用いて合成を行った。ビニル共重合体（ＰＣ−３）の質量平均分子量は３８０００であった。
(1-1) Production Example 1 [Vinyl copolymer (synthesis of PC-1)]
78.0 g of ion-exchanged water is placed in a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen introduction tube (hereinafter, the same reaction vessel is used), and the mixture is uniformly dissolved while stirring, and then the atmosphere is replaced with nitrogen for reaction. The temperature of the system was maintained at 65 ° C. in a warm water bath. Next, 141.7 g of ion-exchanged water, 147.8 g of α-methacryloyl-ω-methoxy-poly (9 mol) oxyethylene, 45.3 g of hydroxyethyl acrylate, 3.9 g of methacrylic acid, and 2- as a chain transfer agent. An aqueous solution in which 1.4 g (molecular weight 78.1) of mercaptoethanol was uniformly dissolved was added dropwise over 2 hours, and 28.6 g of 10% ammonium persulfate was added dropwise over 3 hours. Then, it was held at 65 ° C. for 1 hour to complete the polymerization reaction. After completion of the polymerization reaction, 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 make 40% of the vinyl copolymer (PC-1). An aqueous solution was obtained. When this vinyl copolymer (PC-1) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 41000. The vinyl copolymer (PC-3) is a chain transfer agent in accordance with the synthesis method of Production Example 1 above, by changing the compound used as the structural unit 1, the structural unit 2, and the structural unit 5 and the compounding ratio. The synthesis was carried out using 3-mercaptopropionic acid. The mass average molecular weight of the vinyl copolymer (PC-3) was 38,000.
（１−２）製造例２［ビニル共重合体（ＰＣ−２）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（１１５モル）オキシエチレン１５６．４ｇを反応容器に仕込み、撹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℃に保持した。次に、１％過酸化水素水８．８ｇを３時間かけて滴下するとともに、イオン交換水３９．１ｇにアクリル酸ヒドロキシプロピル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と連鎖移動剤としてチオグリコール酸１．０ｇ（分子量９２．１）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ｐＨ＝６に調整し、イオン交換水にて濃度を４０％に調整して、ビニル共重合体（ＰＣ−２）の４０％水溶液を得た。このビニル共重合体（ＰＣ−２）をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量は４２０００であった。
(1-2) Production Example 2 [Synthesis of Vinyl Copolymer (PC-2)]
76.6 g of ion-exchanged water and 156.4 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (115 mol) oxyethylene were charged into a reaction vessel, dissolved uniformly with stirring, and then the atmosphere was changed. After substitution with nitrogen, the temperature of the reaction system was maintained at 65 ° C. in a warm water bath. Next, 8.8 g of 1% aqueous hydrogen peroxide solution was added dropwise over 3 hours, and 15.6 g of hydroxypropyl acrylate, 3.9 g of acrylate and 19.5 g of methyl acrylate were uniformly added to 39.1 g of ion-exchanged water. The aqueous solution dissolved in the solution was added dropwise over 3 hours, and at the same time, 0.8 g of L-ascorbic acid and 1.0 g of thioglycolic acid (molecular weight 92.1) as a chain transfer agent were dissolved in 7.0 g of ion-exchanged water. The aqueous solution was added dropwise over 4 hours. Then, it was held at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, 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 make 40% of the vinyl copolymer (PC-2). An aqueous solution was obtained. When this vinyl copolymer (PC-2) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 42000.
（２）Ｂ成分（ビニル共重合体の合成）
（２−１）製造例３［ビニル共重合体（ＰＣ−６）の合成］
イオン交換水７５．２ｇ、α−メタクリロイル−ω−ヒドロキシ−ポリ−（２３モル）オキシエチレン１６７．１ｇ、メタクリル酸２２．８ｇ、及び連鎖移動剤として３−メルカプトプロピオン酸１．７ｇ（分子量 １０６．１）を反応容器に仕込み、撹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℃に保持した。次に、１０％過硫酸ナトリウム水溶液２７．５ｇを４時間かけて滴下した。更に６５℃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ｐＨ＝６に調整し、イオン交換水にて濃度を４０％に調整して、ビニル共重合体（ＰＣ−６）の４０％水溶液を得た。このビニル共重合体（ＰＣ−６）をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量は３００００であった。ビニル共重合体（ＰＣ−４，８）は、上記製造例３の合成方法に準拠し、構成単位３、構成単位４、及び構成単位７として使用する化合物及び配合割合を変化させ、連鎖移動剤として３−メルカプトプロピオン酸（分子量 １０６．１）を用いてそれぞれ合成を行った。
(2) Component B (synthesis of vinyl copolymer)
(2-1) Production Example 3 [Synthesis of Vinyl Copolymer (PC-6)]
75.2 g of ion-exchanged water, 167.1 g of α-methacryloyl-ω-hydroxy-poly- (23 mol) oxyethylene, 22.8 g of methacrylic acid, and 1.7 g of 3-mercaptopropionic acid as a chain transfer agent (molecular weight 106. 1) was charged into a reaction vessel and dissolved uniformly with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 65 ° C. in a warm water bath. Next, 27.5 g of a 10% aqueous sodium persulfate solution was added dropwise over 4 hours. Further, the polymerization reaction was completed by holding at 65 ° C. for 2 hours. Then, 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 prepare a 40% aqueous solution of the vinyl copolymer (PC-6). Obtained. When this vinyl copolymer (PC-6) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 30,000. The vinyl copolymer (PC-4, 8) is a chain transfer agent in accordance with the synthesis method of Production Example 3 above, by changing the compound used as the structural unit 3, the structural unit 4, and the structural unit 7 and the compounding ratio. As a result, 3-mercaptopropionic acid (molecular weight 106.1) was used for each synthesis.
（２−２）製造例４［ビニル共重合体（ＰＣ−１０）の合成］
イオン交換水２１０．１ｇ、α−メタクリロイル−ω−ヒドロキシ−ポリ−（６８モル）オキシエチレン１４４．５ｇ、メタクリル酸３８．５ｇ、アクリル酸ヒドロキシエチル１．８ｇ、及び連鎖移動剤として３−メルカプトプロピオン酸２．３ｇを反応容器に仕込み、撹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℃に保持した。次に、１０％過硫酸ナトリウム水溶液３６．６ｇを４時間かけて滴下した。更に６５℃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ｐＨ＝６に調整し、イオン交換水にて濃度を４０％に調整して、ビニル共重合体（ＰＣ−１０）の４０％水溶液を得た。このビニル共重合体（ＰＣ−１０）をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量は３２０００であった。ビニル共重合体（ＰＣ−５及びＰＣ−７）は、上記製造例４の合成方法に準拠し、構成単位３、構成単位４、及び構成単位７、及び構成単位８として使用する化合物及び配合割合を変化させ、連鎖移動剤として３−メルカプトプロピオン酸（分子量 １０６．１）を用いてそれぞれ合成を行った。なお、ビニル共重合体（ＰＣ−９）については、連鎖移動剤を使用せずに合成を行っている。
(2-2) Production Example 4 [Synthesis of Vinyl Copolymer (PC-10)]
210.1 g of ion-exchanged water, 144.5 g of α-methacryloyl-ω-hydroxy-poly- (68 mol) oxyethylene, 38.5 g of methacrylic acid, 1.8 g of hydroxyethyl acrylate, and 3-mercaptopropion as a chain transfer agent. After 2.3 g of acid was charged into a reaction vessel and dissolved uniformly with stirring, the atmosphere was replaced with ethylene, and the temperature of the reaction system was maintained at 65 ° C. in a warm water bath. Next, 36.6 g of a 10% aqueous sodium persulfate solution was added dropwise over 4 hours. Further, the polymerization reaction was completed by holding at 65 ° C. for 2 hours. Then, 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 prepare a 40% aqueous solution of the vinyl copolymer (PC-10). Obtained. When this vinyl copolymer (PC-10) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 32000. The vinyl copolymers (PC-5 and PC-7) conform to the synthesis method of Production Example 4 above, and the compounds and compounding ratios used as the structural unit 3, the structural unit 4, the structural unit 7, and the structural unit 8 are used. , And 3-mercaptopropionic acid (molecular weight 106.1) was used as a chain transfer agent for each synthesis. The vinyl copolymer (PC-9) is synthesized without using a chain transfer agent.
上記により得られたＡ成分としてのビニル共重合体（ＰＣ−１〜ＰＣ−３）を下記の表１に、Ｂ成分としてのビニル共重合体（ＰＣ−４〜ＰＣ−１０）を下記の表２にそれぞれまとめて示す。 The vinyl copolymers (PC-1 to PC-3) as the A component obtained above are shown in Table 1 below, and the vinyl copolymers (PC-4 to PC-10) as the B component are shown in the table below. Each of them is shown in 2.
上記表１及び表２における各構成単位１−８の詳細について説明すると、
＜構成単位１、構成単位３＞
ａ−１：α−メタクリロイル−ω−メトキシ−ポリ(９モル)オキシエチレン
ａ−２：α−(３−メチル−３−ブテニル) −ω−ヒドロキシ−ポリ（１１５モル）オキシエチレン
ａ−３：α−メタリル−ω−ヒドロキシ−ポリ（５３モル）オキシエチレン
ａ−４：α−メタクリロイル−ω−ヒドロキシ−ポリ（２３モル）オキシエチレン
ａ−５：α−メタクリロイル−ω−ヒドロキシ−ポリ（２１モル）オキシエチレンポリ（２モル）オキシプロピレン
ａ−６：α−(３−メチル−３−ブテニル)−ω−ヒドロキシ−ポリ（５０モル）オキシエチレン
ａ−７：α−アリル−ω−メトキシ−ポリ（３３モル）オキシエチレン
ａ−８：α−メタクリロイル−ω−ヒドロキシ−ポリ（６８モル）オキシエチレン
＜構成単位２、構成単位７＞
ｂ−１：アクリル酸ヒドロキシエチル
ｂ−２：アクリル酸ヒドロキシプロピル
ｂ−３：アクリル酸エチル
ｂ−４：アクリル酸メチル
＜構成単位５、構成単位４＞
ｃ−１：メタクリル酸
ｃ−２：アクリル酸
ｃ−３：マレイン酸
＜構成単位６、構成単位８＞
ｄ−１：メタリルスルホン酸ナトリウム
ｄ−２：アクリル酸ブチル
をそれぞれ示すものである。
The details of each structural unit 1-8 in Tables 1 and 2 above will be described.
<Structural unit 1, structural unit 3>
a-1: α-methacryloyl-ω-methoxy-poly (9 mol) oxyethylene a-2: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (115 mol) oxyethylene a-3: α-Metalyl-ω-hydroxy-poly (53 mol) oxyethylene a-4: α-methacryloyl-ω-hydroxy-poly (23 mol) oxyethylene a-5: α-methacryloyl-ω-hydroxy-poly (21 mol) ) Oxyethylene poly (2 mol) Oxypropylene a-6: α- (3-methyl-3-butenyl) -ω-hydroxy-poly (50 mol) Oxyethylene a-7: α-allyl-ω-methoxy-poly (33 mol) Oxyethylene a-8: α-methacryloyl-ω-hydroxy-poly (68 mol) oxyethylene <constituent unit 2, constituent unit 7>
b-1: Hydroxyethyl acrylate
b-2: Hydroxypropyl acrylate b-3: Ethyl acrylate b-4: Methyl acrylate <Constituent unit 5, constituent unit 4>
c-1: Methacrylic acid c-2: Acrylic acid c-3: Maleic acid <Constituent unit 6, constituent unit 8>
d-1: Sodium metallyl sulfonate d-2: Butyl acrylate is shown respectively.
Ａ成分、及びＢ成分であるビニル共重合体のカルボン酸及びその塩の酢酸換算含有割合は、本発明の水硬性組成物用添加剤に含まれるＡ成分及びＢ成分に含まれるカルボン酸及びその塩のカルボキシル基及びその塩を電位差測定して酢酸に換算したときの質量％であり、上記のＡ成分のカルボン酸及びその塩の酢酸換算含有割合の算出と同一であるため、ここでは説明を省略する。これらの測定結果を表１及び表２に示している。 The acetic acid-equivalent content ratio of the carboxylic acid of the vinyl copolymer which is the component A and the component B and its salt is the carboxylic acid contained in the components A and B contained in the additive for the water-hard composition of the present invention and the carboxylic acid thereof. It is the mass% when the carboxyl group of the salt and its salt are measured by the potential difference and converted to acetic acid, which is the same as the calculation of the acetic acid conversion content ratio of the carboxylic acid of component A and its salt. Omit. The measurement results are shown in Tables 1 and 2.
Ａ成分、及びＢ成分であるビニル共重合体の質量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）にて行い、条件を以下のものとした。結果を表１及び表２に示した。 The mass average molecular weights of the vinyl copolymers of the A component and the B component were measured by gel permeation chromatography (GPC), and the conditions were as follows. The results are shown in Tables 1 and 2.
［測定条件］
検出器：示差屈折計（ＲＩ）
カラム：昭和電工株式会社製ＯＨｐａｋ ＳＢ−Ｇ＋ＳＢ−８０６Ｍ ＨＱ＋ＳＢ−８０６Ｍ ＨＱ
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：プルラン（昭和電工株式会社製）
[Measurement condition]
Detector: Differential Refractometer (RI)
Column: Showa Denko OHpak SB-G + SB-806M HQ + SB-806M HQ
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL / min Column temperature: 40 ° C
Standard substance: Pullulan (manufactured by Showa Denko KK)
（３）水硬性組成物用添加剤の調整
合成された表１記載のＡ成分（ＰＣ−１〜ＰＣ−３）、表２に記載のＢ成分（ＰＣ−４〜ＰＣ−１０）、下記に示すＣ成分（Ｃ−１，Ｃ−２）、下記に示すＤ成分（Ｄ−１，Ｄ−２）、及び水を、それぞれ表３に示す割合で配合容器に投入し、撹拌機を用いて十分撹拌混合し、水硬性組成物用添加剤（Ｘ−１〜Ｘ−２３）を調製した（実施例１〜２３）。
(3) Adjustment of Additives for Hydrophilic Composition The synthesized A component (PC-1 to PC-3) shown in Table 1 and B component (PC-4 to PC-10) shown in Table 2 are described below. The C component (C-1, C-2) shown, the D component (D-1, D-2) shown below, and water are added to the compounding container at the ratios shown in Table 3, respectively, and the mixture is used with a stirrer. Additives for water-hard composition (X-1 to X-23) were prepared by sufficiently stirring and mixing (Examples 1 to 23).
同様に、Ａ成分、Ｂ成分、Ｃ成分、Ｄ成分、及び水を、それぞれ表４に示す割合で配合容器に投入し、撹拌機を用いて十分撹拌混合し、水硬性組成物用添加剤（ＲＸ−１〜ＲＸ−５）を調製した（比較例１〜５）。更に、比較例６〜９（ＲＸ−６〜ＲＸ−９）として、市販のＡＥ減水剤 標準形Ｉ種（竹本油脂株式会社製 チューポール ＥＸ６０）、高性能ＡＥ減水剤 標準形Ｉ種（竹本油脂株式会社製 チューポール ＨＰ−１１）、ＡＥ減水剤 遅延形Ｉ種（竹本油脂株式会社製 チューポール ＥＸ６０Ｒ）、及び高性能ＡＥ減水剤 遅延形Ｉ種（竹本油脂株式会社製 商品名 チューポールＨＲ−１１Ｒ）をそれぞれ水硬性組成物用添加剤として使用した。 Similarly, the A component, the B component, the C component, the D component, and water are each added to the compounding container at the ratios shown in Table 4, and the mixture is sufficiently stirred and mixed using a stirrer to prepare an additive for a hydraulic composition (additive for hydraulic composition). RX-1 to RX-5) were prepared (Comparative Examples 1 to 5). Further, as Comparative Examples 6 to 9 (RX-6 to RX-9), a commercially available AE water reducing agent standard type I (Takemoto Oil and Fat Co., Ltd. Chupole EX60) and a high-performance AE water reducing agent standard type I (Takemoto Oil and Fat) Chupole HP-11), AE water reducing agent delayed type I (Takemoto Oil and Fat Co., Ltd. Chupole EX60R), and high-performance AE water reducing agent delayed type I (Takemoto Oil and Fat Co., Ltd. product name Chupole HR- 11R) were used as additives for the water-hard composition, respectively.
実施例１〜２３、及び比較例１〜５において、いずれも水硬性組成物用添加剤１００質量部に対し、水は３１６．７質量部となるように調製されている。すなわち、水硬性組成物用添加剤の濃度（質量％）が２４．０質量％となるように調製されている。 In Examples 1 to 23 and Comparative Examples 1 to 5, the amount of water is 316.7 parts by mass with respect to 100 parts by mass of the additive for hydraulic composition. That is, the concentration (% by mass) of the additive for the hydraulic composition is adjusted to be 24.0% by mass.
上記表３及び表４におけるＣ成分及びＤ成分の詳細について説明すると、
Ｃ−１：グルコン酸ナトリウム
Ｃ−２：クエン酸ナトリウム
Ｄ−１：スクロース
Ｄ−２：フルクトース
をそれぞれ示すものである。
The details of the C component and the D component in Tables 3 and 4 will be described.
C-1: Sodium gluconate C-2: Sodium citrate D-1: Sucrose D-2: Fructose, respectively.
（４）コンクリート組成物（水硬性組成物）の調製
室内温度を４０℃（一部を除く。）に設定した試験室内で、６０Ｌの強制二軸ミキサーに普通ポルトランドセメント（太平洋セメント株式会社製、密度＝３．１６）と、骨材として、細骨材（木更津産陸砂、密度＝２．６０）及び粗骨材（青海産砕石、密度＝２．６７）を順次投入して１０秒間空練りを行った後、水硬性組成物用添加剤（実施例１〜２３、及び比較例１〜９）を加え、更に市販のＡＥ剤であるＡＥ−３００（竹本油脂株式会社製）及び消泡剤であるＡＦＫ−２（竹本油脂株式会社製）を練り混ぜ水とともに投入し、６０秒間練り混ぜて、実施例２４〜実施例６４、及び比較例１０〜３３のコンクリート組成物（水硬性組成物）を調製し、練り混ぜ後、１８０秒間ミキサーで静置したのちに排出し、得られたコンクリート組成物により各種試験を行った。
(4) Preparation of concrete composition (hydraulic composition) In a test room where the room temperature was set to 40 ° C (excluding some), a 60 L forced twin-screw mixer was used for ordinary Portoland Cement (manufactured by Pacific Cement Co., Ltd.). Density = 3.16), fine aggregate (land sand from Kisarazu, density = 2.60) and coarse aggregate (crushed stone from Qinghai, density = 2.67) are sequentially added as aggregates and emptied for 10 seconds. After kneading, additives for hydraulic composition (Examples 1 to 23 and Comparative Examples 1 to 9) are added, and a commercially available AE agent AE-300 (manufactured by Takemoto Oil & Fat Co., Ltd.) and defoaming are added. The agent AFK-2 (manufactured by Takemoto Yushi Co., Ltd.) was added together with kneading water and kneaded for 60 seconds to mix the concrete compositions of Examples 24 to 64 and Comparative Examples 10 to 33 (hydraulic compositions). ) Was prepared, kneaded, allowed to stand in a mixer for 180 seconds, and then discharged, and various tests were carried out using the obtained concrete composition.
なお、比較検討のために、比較例１６、比較例２４、及び比較例３２は、それぞれ室内温度を３０℃に設定した試験室内でコンクリート組成物の調製を行ったものであり、比較例１７、比較例２５、及び比較例３３は、それぞれ室内温度を２０℃に設定した試験室内でコンクリート組成物の調製を行ったものである。 For comparative study, Comparative Example 16, Comparative Example 24, and Comparative Example 32 were prepared in a test room in which the indoor temperature was set to 30 ° C., respectively, and Comparative Example 17 and Comparative Example 17 In Comparative Example 25 and Comparative Example 33, the concrete composition was prepared in a test room in which the room temperature was set to 20 ° C., respectively.
実施例２４〜３６、及び比較例１０〜１７のコンクリート組成物は、表５に示す水、セメント、細骨材、及び粗骨材の配合比率に基づき、水セメント比が５５．０％、細骨材率が４５．４％となるように調整し、目標スランプが“１２±２．５ｃｍ”、かつ、目標空気量が“４．５±１．５％”に設定したものである。 The concrete compositions of Examples 24 to 36 and Comparative Examples 10 to 17 had a water-cement ratio of 55.0% and a fine aggregate ratio based on the blending ratios of water, cement, fine aggregate, and coarse aggregate shown in Table 5. The aggregate ratio was adjusted to 45.4%, the target slump was set to "12 ± 2.5 cm", and the target air volume was set to "4.5 ± 1.5%".
実施例３７〜５１、及び比較例１８〜２５のコンクリート組成物は、表６に示す水、セメント、細骨材、及び粗骨材の配合比率に基づき、水セメント比が５５．０％、細骨材率が４７．０％となるように調整し、目標スランプが“１８±２．５ｃｍ” 、かつ、目標空気量が“４．５±１．５％”となるように設定したものである。 The concrete compositions of Examples 37 to 51 and Comparative Examples 18 to 25 had a water-cement ratio of 55.0% and were fine based on the blending ratios of water, cement, fine aggregate, and coarse aggregate shown in Table 6. The aggregate ratio was adjusted to 47.0%, and the target slump was set to "18 ± 2.5 cm" and the target air volume was set to "4.5 ± 1.5%". be.
実施例５２〜実施例６４、及び比較例２６〜３３のコンクリート組成物は、表７に示す水、セメント、細骨材、及び粗骨材の配合比率に基づき、水セメント比が４８．０％、細骨材率が４５．８％となるように調整し、目標スランプが“２１±１．５ｃｍ”、 かつ、目標空気量が“４．５±１．５％”となるように設定したものである。 The concrete compositions of Examples 52 to 64 and Comparative Examples 26 to 33 have a water-cement ratio of 48.0% based on the blending ratios of water, cement, fine aggregate, and coarse aggregate shown in Table 7. , The fine aggregate ratio was adjusted to 45.8%, and the target slump was set to "21 ± 1.5 cm" and the target air volume was set to "4.5 ± 1.5%". It is a thing.
（５）コンクリート組成物の評価
上記により得られたコンクリート組成物の物性の評価を行った。ここで、スランプ、空気量、ブリーディング率、凝結時間及び圧縮強度の測定は、下記に基づいて実施した。
・スランプ（ｃｍ）：練り混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１０１（２０１４）に準拠して測定した。
・空気量（容積％）：練り混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１２８（２０１９）に準拠して測定した。
・ブリーディング率（％）：練り混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１２３（２０１２）に準拠して測定した。
・凝結時間：練り混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１４７（２０１９）に準拠して測定した。
・圧縮強度（Ｎ／ｍｍ２）：ＪＩＳ−Ａ１１０８（２０１８）に準拠し、供試体寸法を直径１００ｍｍ×高さ２００ｍｍとし、材齢２８日で測定した。
(5) Evaluation of concrete composition The physical properties of the concrete composition obtained as described above were evaluated. Here, the slump, the amount of air, the bleeding rate, the setting time and the compressive strength were measured based on the following.
-Slump (cm): The concrete composition immediately after kneading was measured according to JIS-A1101 (2014).
-Amount of air (% by volume): The concrete composition immediately after kneading was measured in accordance with JIS-A1128 (2019).
Bleeding rate (%): The concrete composition immediately after kneading was measured according to JIS-A1123 (2012).
-Condensing time: The concrete composition immediately after kneading was measured according to JIS-A1147 (2019).
Compressive strength (N / mm 2 ): According to JIS-A1108 (2018), the dimensions of the specimen were 100 mm in diameter x 200 mm in height, and the measurement was performed at a material age of 28 days.
（５−１）目標スランプ１２±２．５ｃｍのコンクリート組成物の評価
実施例２４〜３６、及び比較例１０〜１７のコンクリート組成物について、上記の試験方法により、スランプ、ブリーディング率、凝結時間及び圧縮強度を測定した測定結果を下記の表８、及びその評価のまとめを下記の表９に示す。全ての試験において空気量は４．５±０．５％であることを確認し、練上がり温度は試験室内温度と同温度であることを確認した。また、実施例においては型枠へのコンクリート組成物の打ち込み時のコンクリート組成物温度が３８℃であることを確認した。
(5-1) Evaluation of Concrete Composition with Target Slump 12 ± 2.5 cm For the concrete compositions of Examples 24 to 36 and Comparative Examples 10 to 17, the slump, bleeding rate, setting time and setting time were determined by the above test methods. The measurement results obtained by measuring the compressive strength are shown in Table 8 below, and the summary of the evaluation is shown in Table 9 below. In all the tests, it was confirmed that the amount of air was 4.5 ± 0.5%, and the kneading temperature was confirmed to be the same as the test chamber temperature. Further, in the examples, it was confirmed that the temperature of the concrete composition at the time of driving the concrete composition into the formwork was 38 ° C.
表９において、スランプ保持性、ブリーディング率、及び凝結時間の評価は以下の基準に基づいて行った。 In Table 9, the slump retention, bleeding rate, and settling time were evaluated based on the following criteria.
＜スランプ保持性＞
Ｓ：練り上がりから５分後のスランプ値とスランプとの差が±０〜２．５ｃｍ以下
Ａ：練り上がりから５分後のスランプ値とスランプとの差が±２．５ｃｍ超〜５．０ｃｍ以下
Ｂ：練り上がりから５分後のスランプ値とスランプとの差が±５．０ｃｍ超〜７．５ｃｍ以下
Ｃ：練り上がりから５分後のスランプ値とスランプとの差が±７．５ｃｍ超
<Slump retention>
S: Difference between slump value and slump 5 minutes after kneading is ± 0 to 2.5 cm or less A: Difference between slump value and slump 5 minutes after kneading is more than ± 2.5 cm to 5.0 cm Below B: The difference between the slump value and the slump 5 minutes after kneading is more than ± 5.0 cm to 7.5 cm or less C: The difference between the slump value and the slump 5 minutes after kneading is more than ± 7.5 cm
＜ブリーディング率＞
Ｓ：比較例１７の測定結果に対して±０．５％以下
Ａ：比較例１７の測定結果に対して±０．５％超〜１．０％以下
Ｂ：比較例１７の測定結果に対して±１．０％超〜１．５％以下
Ｃ：比較例１７の測定結果に対して±１．５％超
<Bleeding rate>
S: ± 0.5% or less with respect to the measurement result of Comparative Example 17 A: More than ± 0.5% to 1.0% or less with respect to the measurement result of Comparative Example 17 B: With respect to the measurement result of Comparative Example 17 More than ± 1.0% to less than 1.5% C: More than ± 1.5% of the measurement results of Comparative Example 17
＜凝結時間＞
Ｓ：比較例１７の測定結果に対して±３０分以内
Ａ：比較例１７の測定結果に対して±３０分超〜１時間以下
Ｂ：比較例１７の測定結果に対して±１時間超〜２時間以下
Ｃ：比較例１７の測定結果に対して±２時間超
<Condensation time>
S: Within ± 30 minutes with respect to the measurement result of Comparative Example 17 A: More than ± 30 minutes to 1 hour or less with respect to the measurement result of Comparative Example 17 B: More than ± 1 hour with respect to the measurement result of Comparative Example 17 2 hours or less C: More than ± 2 hours with respect to the measurement result of Comparative Example 17
（５−２）目標スランプ１８±２．５ｃｍのコンクリート組成物の評価
実施例３７〜５１、及び比較例１８〜２５のコンクリート組成物について、上記の試験方法により、スランプ、ブリーディング率、凝結時間及び圧縮強度を測定した測定結果を下記の表１０及び表１１に示す。全ての試験において空気量は４．５±０．５％であることを確認し、練上がり温度は試験室内温度と同温度であることを確認した。また、実施例においては型枠へのコンクリート組成物の打ち込み時のコンクリート組成物温度が３８℃であることを確認した。
(5-2) Evaluation of Concrete Composition with Target Slump 18 ± 2.5 cm For the concrete compositions of Examples 37 to 51 and Comparative Examples 18 to 25, the slump, bleeding rate, setting time and setting time were determined by the above test methods. The measurement results of measuring the compressive strength are shown in Tables 10 and 11 below. In all the tests, it was confirmed that the amount of air was 4.5 ± 0.5%, and the kneading temperature was confirmed to be the same as the test chamber temperature. Further, in the examples, it was confirmed that the temperature of the concrete composition at the time of driving the concrete composition into the formwork was 38 ° C.
表１１において、スランプ保持性、ブリーディング率、及び凝結時間の評価は以下の基準に基づいて行った。 In Table 11, the slump retention, bleeding rate, and settling time were evaluated based on the following criteria.
＜スランプ保持性＞
Ｓ：練り上がりから５分後のスランプ値とスランプとの差が±０〜２．５ｃｍ以下
Ａ：練り上がりから５分後のスランプ値とスランプとの差が±２．５ｃｍ超〜５．０ｃｍ以下
Ｂ：練り上がりから５分後のスランプ値とスランプとの差が±５．０ｃｍ超〜７．５ｃｍ以下
Ｃ：練り上がりから５分後のスランプ値とスランプとの差が±７．５ｃｍ超
<Slump retention>
S: Difference between slump value and slump 5 minutes after kneading is ± 0 to 2.5 cm or less A: Difference between slump value and slump 5 minutes after kneading is more than ± 2.5 cm to 5.0 cm Below B: The difference between the slump value and the slump 5 minutes after kneading is more than ± 5.0 cm to 7.5 cm or less C: The difference between the slump value and the slump 5 minutes after kneading is more than ± 7.5 cm
＜ブリーディング率＞
Ｓ：比較例２５の測定結果に対して±０．５％以下
Ａ：比較例２５の測定結果に対して±０．５％超〜１．０％以下
Ｂ：比較例２５の測定結果に対して±１．０％超〜１．５％以下
Ｃ：比較例２５の測定結果に対して±１．５％超
<Bleeding rate>
S: ± 0.5% or less with respect to the measurement result of Comparative Example 25 A: More than ± 0.5% to 1.0% or less with respect to the measurement result of Comparative Example 25 B: With respect to the measurement result of Comparative Example 25 More than ± 1.0% to less than 1.5% C: More than ± 1.5% of the measurement results of Comparative Example 25
＜凝結時間＞
Ｓ：比較例２５の測定結果に対して±３０分以内
Ａ：比較例２５の測定結果に対して±３０分超〜１時間以下
Ｂ：比較例２５の測定結果に対して±１時間超〜２時間以下
Ｃ：比較例２５の測定結果に対して±２時間超
<Condensation time>
S: Within ± 30 minutes with respect to the measurement result of Comparative Example 25 A: More than ± 30 minutes to 1 hour or less with respect to the measurement result of Comparative Example 25 B: More than ± 1 hour with respect to the measurement result of Comparative Example 25 2 hours or less C: More than ± 2 hours with respect to the measurement result of Comparative Example 25
（５−３）目標スランプ２１±１．５ｃｍのコンクリート組成物の評価
実施例５２〜６４、及び比較例２６〜３３のコンクリート組成物について、上記の試験方法により、スランプ、ブリーディング率、凝結時間及び圧縮強度を測定した測定結果を下記の表１２及び表１３に示す。全ての試験において空気量は４．５±０．５％であることを確認し、練上がり温度は試験室内温度と同温度であることを確認した。また、実施例においては型枠へのコンクリート組成物の打ち込み時のコンクリート組成物温度が３８℃であることを確認した。
(5-3) Evaluation of Concrete Composition with Target Slump 21 ± 1.5 cm For the concrete compositions of Examples 52 to 64 and Comparative Examples 26 to 33, the slump, bleeding rate, setting time and setting time were determined by the above test methods. The measurement results of measuring the compressive strength are shown in Tables 12 and 13 below. In all the tests, it was confirmed that the amount of air was 4.5 ± 0.5%, and the kneading temperature was confirmed to be the same as the test chamber temperature. Further, in the examples, it was confirmed that the temperature of the concrete composition at the time of driving the concrete composition into the formwork was 38 ° C.
表１３において、スランプ保持性、ブリーディング率、及び凝結時間の評価は以下の基準に基づいて行った。 In Table 13, the slump retention, bleeding rate, and settling time were evaluated based on the following criteria.
＜スランプ保持性＞
Ｓ：練り上がりから５分後のスランプ値とスランプとの差が±０〜２．５ｃｍ以下
Ａ：練り上がりから５分後のスランプ値とスランプとの差が±２．５ｃｍ超〜５．０ｃｍ以下
Ｂ：練り上がりから５分後のスランプ値とスランプとの差が±５．０ｃｍ超〜７．５ｃｍ以下
Ｃ：練り上がりから５分後のスランプ値とスランプとの差が±７．５ｃｍ超
<Slump retention>
S: Difference between slump value and slump 5 minutes after kneading is ± 0 to 2.5 cm or less A: Difference between slump value and slump 5 minutes after kneading is more than ± 2.5 cm to 5.0 cm Below B: The difference between the slump value and the slump 5 minutes after kneading is more than ± 5.0 cm to 7.5 cm or less C: The difference between the slump value and the slump 5 minutes after kneading is more than ± 7.5 cm
＜ブリーディング率＞
Ｓ：比較例３３の測定結果に対して±０．５％以下
Ａ：比較例３３の測定結果に対して±０．５％超〜１．０％以下
Ｂ：比較例３３の測定結果に対して±１．０％超〜１．５％以下
Ｃ：比較例３３の測定結果に対して±１．５％超
<Bleeding rate>
S: ± 0.5% or less with respect to the measurement result of Comparative Example 33 A: More than ± 0.5% to 1.0% or less with respect to the measurement result of Comparative Example 33 B: With respect to the measurement result of Comparative Example 33 More than ± 1.0% to less than 1.5% C: More than ± 1.5% with respect to the measurement result of Comparative Example 33
＜凝結時間＞
Ｓ：比較例３３の測定結果に対して±３０分以内
Ａ：比較例３３の測定結果に対して±３０分超〜１時間以下
Ｂ：比較例３３の測定結果に対して±１時間超〜２時間以下
Ｃ：比較例３３の測定結果に対して±２時間超
<Condensation time>
S: Within ± 30 minutes with respect to the measurement result of Comparative Example 33 A: More than ± 30 minutes to 1 hour or less with respect to the measurement result of Comparative Example 33 B: More than ± 1 hour with respect to the measurement result of Comparative Example 33 2 hours or less C: More than ± 2 hours with respect to the measurement result of Comparative Example 33
（６）評価結果
上記表８〜表１３に示す結果から明らかなように、４０℃環境下において、実施例１〜１２（Ｘ−１〜Ｘ−１２）を同時添加型の添加剤として使用したコンクリート組成物は、２０℃環境下において現行のＡＥ減水剤 標準形Ｉ種（チューポールＥＸ６０）または高性能ＡＥ減水剤 標準形Ｉ種（チューポールＨＰ−１１）を使用したコンクリート組成物と比較し、同等以上のスランプ保持性、ブリーディング率、及び凝結時間（以下、「スランプ保持性等」と称す。）を示すことが認められる（実施例２４〜２７、実施例３７〜４０、及び実施例５２〜５５参照）。
(6) Evaluation Results As is clear from the results shown in Tables 8 to 13 above, Examples 1 to 12 (X-1 to X-12) were used as simultaneous addition type additives in an environment of 40 ° C. The concrete composition is compared with the concrete composition using the current AE water reducing agent standard type I (Chupol EX60) or the high performance AE water reducing agent standard type I (Chupole HP-11) in an environment of 20 ° C. , Equivalent or higher slump retention, bleeding rate, and setting time (hereinafter referred to as "slump retention, etc.") are recognized (Examples 24 to 27, Examples 37 to 40, and Example 52). See ~ 55).
なお、比較例１５，２３，３１に示されるように、現在使用されているＡＥ減水剤 遅延型Ｉ種（チューポールＥＸ６０Ｒ）または高性能ＡＥ減水剤 遅延型Ｉ種（チューポールＨＰ−１１Ｒ）を４０℃環境下のコンクリート組成物に対して使用した場合、スランプ保持性等において十分な効果は示されないことが確認される。 As shown in Comparative Examples 15, 23 and 31, the currently used AE water reducing agent delayed type I (Chupole EX60R) or high-performance AE water reducing agent delayed type I (Chupole HP-11R) is used. It is confirmed that when it is used for a concrete composition in an environment of 40 ° C., it does not show a sufficient effect on slump retention and the like.
本発明の水硬性組成物用添加剤は、３５℃以上の高温環境下においてコンクリート組成物等の水硬性組成物を調製する際に添加される同時添加型の添加剤として利用することができる。
The additive for a hydraulic composition of the present invention can be used as a simultaneous addition type additive added when preparing a hydraulic composition such as a concrete composition in a high temperature environment of 35 ° C. or higher.
Claims (8)
前記Ａ成分、前記Ｂ成分、前記Ｃ成分、及び前記Ｄ成分の含有割合の合計を１００質量％とした場合において、
前記Ａ成分を５〜６５質量％、前記Ｂ成分を１５〜７５質量％、前記Ｃ成分を１０〜７０質量％、及び前記Ｄ成分を１０〜７０質量％の割合でそれぞれ含有する水硬性組成物用添加剤。
Ａ成分：下記の化１で示される構成単位１及び下記の構成単位２を有し、
前記Ａ成分において構成単位１及び構成単位２の合計１００質量％に対し、前記構成単位１を７０〜９５質量％、及び前記構成単位２を５〜３０質量％の割合でそれぞれ含有し、前記Ａ成分中のカルボン酸及びその塩の酢酸換算含有割合が０．１〜４．０質量％であり、かつ、質量平均分子量が１０００〜２０００００であるビニル共重合体
構成単位１：
構成単位２：
（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成される構成単位
Ｂ成分：下記の化２で示される構成単位３及び下記の構成単位４を有し、
前記Ｂ成分において構成単位３及び構成単位４の合計１００質量％に対し、前記構成単位３を６５〜９５質量％、及び前記構成単位４を５〜３５質量％の割合でそれぞれ含有し、前記Ｂ成分中のカルボン酸及びその塩の酢酸換算含有割合が４．０質量％を超え４０．０質量％以下であり、かつ、質量平均分子量が１０００〜２０００００であるビニル共重合体
構成単位３：
構成単位４：
不飽和カルボン酸及びその塩から選ばれる少なくとも一つから形成される構成単位
Ｃ成分：オキシカルボン酸及びその塩から選ばれる少なくとも一つ
Ｄ成分：糖類 An additive for a hydraulic composition containing the following A component, the following B component, the following C component, and the following D component.
When the total content of the A component, the B component, the C component, and the D component is 100% by mass,
A hydraulic composition containing 5 to 65% by mass of the A component, 15 to 75% by mass of the B component, 10 to 70% by mass of the C component, and 10 to 70% by mass of the D component, respectively. Additives for.
Component A: It has the structural unit 1 shown in Chemical formula 1 below and the structural unit 2 below.
In the component A, the structural unit 1 is contained in an amount of 70 to 95% by mass and the structural unit 2 is contained in a proportion of 5 to 30% by mass with respect to a total of 100% by mass of the structural unit 1 and the structural unit 2. Vinyl copolymer constituent unit 1: The acetic acid-equivalent content ratio of the carboxylic acid and its salt in the components is 0.1 to 4.0% by mass, and the mass average molecular weight is 1000 to 200,000.
Structural unit 2:
A structural unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate. It has a structural unit 3 shown and a structural unit 4 below.
In the B component, the constituent unit 3 is contained in an amount of 65 to 95% by mass and the constituent unit 4 is contained in a proportion of 5 to 35% by mass with respect to a total of 100% by mass of the constituent unit 3 and the constituent unit 4, respectively. Vinyl copolymer structural unit 3: The acetic acid-equivalent content ratio of the carboxylic acid and its salt in the components is more than 4.0% by mass and 40.0% by mass or less, and the mass average molecular weight is 1000 to 200,000.
Structural unit 4:
Constituent unit formed from at least one selected from unsaturated carboxylic acid and its salt C component: At least one selected from oxycarboxylic acid and its salt D component: Sugar
下記の構成単位５、及び下記の構成単位６を更に有し、
前記Ａ成分中に前記構成単位５を０．１〜２０質量％、及び前記構成単位６を０〜１０質量％の割合でそれぞれ含有する請求項１に記載の水硬性組成物用添加剤。
構成単位５：
不飽和カルボン酸及びその塩から選ばれる少なくとも一つから形成される構成単位
構成単位６：
分子中にビニル基を有する単量体から形成される構成単位 The A component is
It further has the following structural unit 5 and the following structural unit 6.
The additive for a hydraulic composition according to claim 1, wherein the constituent unit 5 is contained in the component A in an amount of 0.1 to 20% by mass and the constituent unit 6 is contained in a proportion of 0 to 10% by mass.
Constituent unit 5:
Constituent units formed from at least one selected from unsaturated carboxylic acids and salts thereof Constituent units 6:
A building block formed from a monomer having a vinyl group in the molecule
下記の構成単位７、及び下記の構成単位８を更に有し、
前記Ｂ成分中に前記構成単位７を０〜５質量％、及び前記構成単位８を０〜１０質量％の割合でそれぞれ含有する請求項１または２に記載の水硬性組成物用添加剤。
構成単位７：
（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸エチル、及び（メタ）アクリル酸メチルから選ばれる少なくとも一つから形成される構成単位
構成単位８：
分子中にビニル基を有する単量体から形成される構成単位 The B component is
It further has the following structural unit 7 and the following structural unit 8.
The additive for a water-hard composition according to claim 1 or 2, wherein the constituent unit 7 is contained in the component B in an amount of 0 to 5% by mass, and the constituent unit 8 is contained in a proportion of 0 to 10% by mass, respectively.
Structural unit 7:
A structural unit formed from at least one selected from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, and methyl (meth) acrylate.
A building block formed from a monomer having a vinyl group in the molecule
グルコン酸及びグルコン酸ナトリウム塩から選ばれる少なくとも一つである請求項１〜４のいずれか一項に記載の水硬性組成物用添加剤。 The C component is
The additive for a hydraulic composition according to any one of claims 1 to 4, which is at least one selected from gluconic acid and sodium gluconate salt.
スクロースである請求項１〜５のいずれか一項に記載の水硬性組成物用添加剤。 The D component is
The additive for a hydraulic composition according to any one of claims 1 to 5, which is sucrose.
（１）型枠への水硬性組成物の打ち込み時の水硬性組成物温度が２５℃以上
（２）型枠への水硬性組成物の打ち込み時の日平均気温が２５℃以上
（３）型枠への水硬性組成物の打ち込み日の最高気温が３０℃以上 The additive for a hydraulic composition according to any one of claims 1 to 6, which is used under at least one use condition selected from the following (1) to (3).
(1) The water-hard composition temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (2) The daily average temperature at the time of driving the water-hard composition into the mold is 25 ° C or higher (3) type The maximum temperature on the day when the water-hard composition is driven into the frame is 30 ° C or higher.
セメントを含有する結合材と、
水と、
細骨材と、
粗骨材と
を含有する水硬性組成物。
The additive for a hydraulic composition according to any one of claims 1 to 7, and the additive for a hydraulic composition.
Cement-containing binder and
water and,
Fine aggregate and
A hydraulic composition containing a coarse aggregate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021109798A (en) * | 2020-01-09 | 2021-08-02 | 株式会社大林組 | Additive for hydraulic composition, and hydraulic composition |
| JP7393762B2 (en) | 2020-01-09 | 2023-12-07 | 株式会社大林組 | Additives for hydraulic compositions and hydraulic compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4709359B2 (en) | 1999-09-27 | 2011-06-22 | 太平洋セメント株式会社 | Hydraulic composition |
| JP4448274B2 (en) | 2002-01-23 | 2010-04-07 | 株式会社日本触媒 | Method of constructing cement admixture and cement composition |
| WO2009131240A1 (en) | 2008-04-24 | 2009-10-29 | ダブリュー・アール・グレイス・アンド・カンパニーーコネチカット | Concrete or mortar admixture composition |
| WO2016067826A1 (en) | 2014-10-31 | 2016-05-06 | 竹本油脂株式会社 | Post-mixing admixture for concrete |
| JP6739784B2 (en) | 2016-04-28 | 2020-08-12 | 竹本油脂株式会社 | Post-additive admixture for concrete and method for maintaining concrete fluidity |
| JP6893821B2 (en) | 2016-08-29 | 2021-06-23 | 株式会社日本触媒 | Cement Additives and Cement Compositions |
| JP7308485B2 (en) | 2019-09-20 | 2023-07-14 | 株式会社竹中工務店 | Concrete admixture, concrete composition, casting method for concrete composition, and mass concrete |
| JP7393762B2 (en) | 2020-01-09 | 2023-12-07 | 株式会社大林組 | Additives for hydraulic compositions and hydraulic compositions |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021109798A (en) * | 2020-01-09 | 2021-08-02 | 株式会社大林組 | Additive for hydraulic composition, and hydraulic composition |
| JP7303525B2 (en) | 2020-01-09 | 2023-07-05 | 株式会社大林組 | ADDITIVE FOR HYDRAULIC COMPOSITION, AND HYDRAULIC COMPOSITION |
| JP7393762B2 (en) | 2020-01-09 | 2023-12-07 | 株式会社大林組 | Additives for hydraulic compositions and hydraulic compositions |
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