JP6765641B2 - Shrinkage reducer for cement and cement composition - Google Patents
Shrinkage reducer for cement and cement composition Download PDFInfo
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- JP6765641B2 JP6765641B2 JP2017052096A JP2017052096A JP6765641B2 JP 6765641 B2 JP6765641 B2 JP 6765641B2 JP 2017052096 A JP2017052096 A JP 2017052096A JP 2017052096 A JP2017052096 A JP 2017052096A JP 6765641 B2 JP6765641 B2 JP 6765641B2
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- 239000004568 cement Substances 0.000 title claims description 74
- 239000003638 chemical reducing agent Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000005227 gel permeation chromatography Methods 0.000 claims description 14
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
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- 239000004570 mortar (masonry) Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
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- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 230000001603 reducing effect Effects 0.000 description 11
- 230000007423 decrease Effects 0.000 description 9
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
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- 239000004567 concrete Substances 0.000 description 8
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- 238000010998 test method Methods 0.000 description 4
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- 239000004480 active ingredient Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
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- 239000013110 organic ligand Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001204 arachidyl 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])[H] 0.000 description 2
- 125000002511 behenyl 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])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 125000002704 decyl group Chemical group [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])* 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 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
- 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
- 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000243 solution Substances 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
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 125000002889 tridecyl 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])[H] 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002463 lignoceryl 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])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002819 montanyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001802 myricyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Description
本発明は、セメント用収縮低減剤およびそれを含むセメント組成物に関する。詳しくは、セメント組成物の乾燥収縮を低減することでひび割れを抑制し、圧縮強度および耐凍害性が低下せず、さらに作業性が低下しないセメント用収縮低減剤およびセメント組成物に関する。 The present invention relates to a shrinkage reducing agent for cement and a cement composition containing the same. More specifically, the present invention relates to a shrinkage reducing agent for cement and a cement composition, which suppresses cracking by reducing the drying shrinkage of the cement composition, does not lower the compressive strength and frost damage resistance, and does not lower the workability.
近年、建造物の耐震性確保や長寿命化が求められており、コンクリートの耐久性に対する要求が高まっている。コンクリート等のセメント組成物では、ひび割れの発生により、セメント組成物の早期劣化を引き起こすことが課題となっている。セメント組成物のひび割れを起こす原因の一つとして、硬化後にセメント組成物内部に残った未反応水の逸散に伴い生じる、乾燥収縮が知られている。このような乾燥収縮は、セメント組成物のひび割れに加えて、耐久性が低下するなどの悪影響を及ぼすため、乾燥収縮量を低減する目的で、セメント用乾燥収縮低減剤が使用されている。 In recent years, there has been a demand for ensuring earthquake resistance and extending the life of buildings, and there is an increasing demand for the durability of concrete. In cement compositions such as concrete, it is a problem that cracks occur to cause early deterioration of the cement composition. As one of the causes of cracking of the cement composition, it is known that drying shrinkage occurs due to the dissipation of unreacted water remaining inside the cement composition after curing. Such drying shrinkage has an adverse effect such as a decrease in durability in addition to cracking of the cement composition. Therefore, a drying shrinkage reducing agent for cement is used for the purpose of reducing the amount of drying shrinkage.
従来のセメント用乾燥収縮低減剤としては、例えばアルキレンオキシド誘導体等が知られているものの（特許文献１）、乾燥収縮低減剤を多く添加すると、セメント組成物の圧縮強度が低下する場合があった。そのため、乾燥収縮効果と圧縮強度を両立させる収縮低減剤として、１〜６価の脂肪族アルコールアルキレンオキシド付加物が提案されている（特許文献２）。 As a conventional dry shrinkage reducing agent for cement, for example, an alkylene oxide derivative is known (Patent Document 1), but if a large amount of the dry shrinkage reducing agent is added, the compressive strength of the cement composition may decrease. .. Therefore, a 1- to hexavalent aliphatic alcohol alkylene oxide adduct has been proposed as a shrinkage reducing agent that achieves both a drying shrinkage effect and a compressive strength (Patent Document 2).
一方、寒冷地に施工されるセメント組成物では、細孔中の水が凍結と融解を繰り返すことにより体積変化が起こり、内部組織が破壊される凍害の問題が生じる。乾燥収縮低減剤の使用により、乾燥収縮低減剤を使用しない場合と比較して、凍害が促進される傾向があり、添加量を多くできない場合には、所望の乾燥収縮低減効果が得られないという問題があった。 On the other hand, in a cement composition constructed in a cold region, the water in the pores is repeatedly frozen and thawed to cause a volume change, which causes a problem of frost damage in which the internal structure is destroyed. It is said that the use of the dry shrinkage reducing agent tends to promote frost damage as compared with the case where the dry shrinkage reducing agent is not used, and if the addition amount cannot be increased, the desired drying shrinkage reducing effect cannot be obtained. There was a problem.
これらの問題を解決するために、２０℃にて水に対する飽和濃度が５重量％未満である非水溶性の化合物とＨＬＢ値が９以上のポリオキシアルキレン誘導体からなる乾燥収縮低減剤が提案されている（特許文献３）。この収縮低減剤を使用した場合、凍害による影響が小さく、良好な耐久性を有するセメント組成物が得られる。 In order to solve these problems, a drying shrinkage reducing agent consisting of a water-insoluble compound having a saturation concentration of less than 5% by weight with respect to water at 20 ° C. and a polyoxyalkylene derivative having an HLB value of 9 or more has been proposed. (Patent Document 3). When this shrinkage reducing agent is used, a cement composition that is less affected by frost damage and has good durability can be obtained.
更にまた、建造物の高層化に伴い、セメント組成物の高強度化が進んでいることにより、組成物中の水分量をできるだけ抑えるために、セメント組成物を施工する際の粘性が高いという問題が生じている。そのため、作業性の観点から、セメント組成物のスランプ値を維持したまま、フロー値を大きくした「粘性」の低いセメント組成物が求められている。しかし、乾燥収縮低減性、圧縮強度、耐凍害性および作業性のいずれの特性も優れたセメント組成物はこれまでなかった。 Furthermore, as the strength of cement compositions is increasing with the increase in the number of buildings, there is a problem that the viscosity of cement compositions is high in order to suppress the amount of water in the compositions as much as possible. Is occurring. Therefore, from the viewpoint of workability, there is a demand for a cement composition having a large flow value and a low "viscosity" while maintaining the slump value of the cement composition. However, no cement composition has been excellent in all of the properties of reducing drying shrinkage, compressive strength, frost damage resistance and workability.
本発明の課題は、良好な収縮低減効果を発現することでひび割れを抑制するとともに、耐凍害性と圧縮強度が低下せず、またセメント組成物の粘性が低く施工時の作業性が低下しないセメント用収縮低減剤を提供することである。 The subject of the present invention is a cement that suppresses cracks by exhibiting a good shrinkage reducing effect, does not reduce frost damage resistance and compressive strength, and has low viscosity of the cement composition and does not reduce workability during construction. Is to provide a shrinkage reducing agent.
本発明者らは、上記の課題を解決するために鋭意研究を重ねた結果、特定のポリオキシアルキレン誘導体を有効成分として含む収縮低減剤が、上記の課題を解決することの知見を得て、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained the finding that a shrinkage reducing agent containing a specific polyoxyalkylene derivative as an active ingredient solves the above problems. The present invention has been completed.
すなわち、本発明は、次の[１]および[２]である。
[１] 下記成分（Ａ）と成分（Ｂ）とを９０．０〜９９．９質量部：１０．０〜０．１質量部の割合で含有することを特徴とする、セメント用収縮低減剤。
成分（Ａ）：
下記式（１）で表されるポリオキシアルキレン誘導体
Ｒ１Ｏ−（ＡＯ）ｍ−Ｒ２
・・・（１）
（式（１）中、
Ｒ１は炭素数１〜３０の炭化水素基であり、
Ｒ２は水素原子およびメチル基からなる群より選ばれた一種以上を表し、
ＡＯは炭素数３〜４のオキシアルキレン基であり、
ｍは前記オキシアルキレン基ＡＯの平均付加モル数であり、ｍ＝１〜３０の数を示す。）
成分（Ｂ）：
下記式（２）で表され、かつゲル浸透クロマトグラフィー測定により求められるクロマトグラムから算出されるＭＨとＭＬとが下記式（３）の関係を満足するポリオキシアルキレン誘導体
Ｒ３Ｏ−（ＰＯ）ｎ−Ｈ ・・・（２）
（式（２）中、
Ｒ３は炭素数１〜２２の炭化水素基であり、
ＰＯは炭素数３のオキシアルキレン基を表し、
ｎは３５以上の数を示す。）
０．３５≦ＭＬ／ＭＨ≦０．７５ ・・・（３）
（式（３）中、
前記クロマトグラム上の屈折率強度が最大となる極大点ＫからベースラインＢへの垂線の長さをＬとし、屈折率強度がＬ／２となるクロマトグラム上の２点のうち溶出時間が早いほうを点Ｏとし、溶出時間が遅いほうを点Ｑとし、点Ｏと点Ｑを結ぶ直線Ｇと前記極大点Ｋから前記ベースラインへ引いた垂線との交点をＰとしたとき、点Ｏと交点Ｐの距離をＭＨとし、点Ｑと交点Ｐの距離をＭＬとする。）
That is, the present invention is the following [1] and [2].
[1] A shrinkage reducing agent for cement, which comprises the following component (A) and component (B) in a ratio of 90.0 to 99.9 parts by mass: 10.0 to 0.1 parts by mass. ..
Ingredient (A):
Polyoxyalkylene derivative represented by the following formula (1)
R 1 O- (AO) m- R 2
... (1)
(In equation (1),
R 1 is a hydrocarbon group having 1 to 30 carbon atoms.
R 2 represents one or more selected from the group consisting of hydrogen atom and methyl group.
AO is an oxyalkylene group having 3 to 4 carbon atoms.
m is the average number of moles of the oxyalkylene group AO added, and indicates the number of m = 1 to 30. )
Ingredient (B):
Represented by the following formula (2), and a polyoxyalkylene derivative and a M H and M L satisfy the relation of the following formula (3) calculated from the chromatogram obtained by the gel permeation chromatography measurement
R 3 O- (PO) n- H ... (2)
(In equation (2),
R 3 is a hydrocarbon group having 1 to 22 carbon atoms.
PO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 35 or more. )
0.35 ≦ M L / M H ≦ 0.75 ··· (3)
(In equation (3),
The length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L, and the dissolution time is the fastest among the two points on the chromatogram where the refractive index intensity is L / 2. When the point O is defined as the point O, the one with the slower dissolution time is defined as the point Q, and the intersection of the straight line G connecting the point O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is P, the point O and the distance of the intersection point P and M H, the distance between the point Q and the point of intersection P and M L. )
[２] セメント１００質量部に対し、［１］のセメント用収縮低減剤０．１〜１０質量部を含有することを特徴とする、セメント組成物。 [2] A cement composition comprising 0.1 to 10 parts by mass of the shrinkage reducing agent for cement according to [1] with respect to 100 parts by mass of cement.
本発明のセメント用収縮低減剤を用いることにより、セメント組成物の乾燥収縮が低減されるためひび割れが防止され、高い耐凍害性と圧縮強度を示し、かつセメント組成物の粘性が低く作業性が良好であるため、耐久性と施工性に優れたセメント組成物が得られる。 By using the shrinkage reducing agent for cement of the present invention, the drying shrinkage of the cement composition is reduced, so that cracking is prevented, high frost damage resistance and compressive strength are exhibited, and the viscosity of the cement composition is low and workability is improved. Since it is good, a cement composition having excellent durability and workability can be obtained.
本発明で示されるセメント用収縮低減剤は、下記式（１）で示されるポリオキシアルキレン誘導体（成分（Ａ））を有効成分として含む。
Ｒ１Ｏ−（ＡＯ）ｍ−Ｒ２
・・・（１）
The shrinkage reducing agent for cement represented by the present invention contains a polyoxyalkylene derivative (component (A)) represented by the following formula (1) as an active ingredient.
R 1 O- (AO) m- R 2
... (1)
式（１）において、Ｒ１は、炭素数１〜３０の炭化水素基から選ばれる一種または二種以上である。Ｒ１の炭素数が３０より大きいと、モルタル中への分散性が低下し、収縮低減性および耐凍害性が低下するので、３０以下とするが、２２以下が更に好ましい。また、Ｒ１の炭素数は１以上であるが、８以上が更に好ましく、１２以上が特に好ましい。Ｒ１としては、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、イソステアリル基、イコシル基、ドコシル基、テトラコシル基、オクタコシル基、トリアコンチル基などが挙げられる。
式（１）において、Ｒ２は、水素原子およびメチル基からなる群より選ばれる一種以上である。好ましくはＲ２が水素原子のみである。Ｒ２における炭素数が１より大きいと、モルタルへの分散性が低下し、収縮低減性および耐凍害性が低下する。
In the formula (1), R 1 is one or more selected from hydrocarbon groups having 1 to 30 carbon atoms. When the number of carbon atoms of R 1 is larger than 30, the dispersibility in the mortar is lowered, and the shrinkage reducing property and the frost damage resistance are lowered. Therefore, the number is 30 or less, but 22 or less is more preferable. The carbon number of R 1 is 1 or more, but 8 or more is more preferable, and 12 or more is particularly preferable. Examples of R 1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group and isosetyl group. , Octadecyl group, isostearyl group, icosyl group, docosyl group, tetracosyl group, octacosyl group, triacontyl group and the like.
In formula (1), R 2 is one or more selected from the group consisting of a hydrogen atom and a methyl group. Preferably R 2 is only a hydrogen atom. It is greater than 1 the number of carbon atoms in R 2, decreases the dispersibility of the mortar shrinkage reducing property and freeze-thaw resistance is lowered.
式（１）において、ＡＯは炭素数３〜４のオキシアルキレン基であり、例えばオキシプロピレン基、オキシブチレン基が挙げられ、好ましくは炭素数３のオキシプロピレン基である。ＡＯを構成するオキシアルキレン基の炭素数が２以下である場合、耐凍害性が低下する。ＡＯを構成するオキシアルキレン基の炭素数が５以上である場合、収縮低減性が低下する。 In the formula (1), AO is an oxyalkylene group having 3 to 4 carbon atoms, and examples thereof include an oxypropylene group and an oxybutylene group, preferably an oxypropylene group having 3 carbon atoms. When the number of carbon atoms of the oxyalkylene group constituting AO is 2 or less, the frost damage resistance is lowered. When the number of carbon atoms of the oxyalkylene group constituting AO is 5 or more, the shrinkage reducing property is lowered.
式（１）において、オキシアルキレン基の平均付加モル数を表すｍは１〜３０であり、好ましくは１〜２５であり、より好ましくは５〜２０である。オキシアルキレン基の平均付加モル数を表すｍが１未満である場合、収縮低減性が低下し、ｍが３０より大きい場合、耐凍害性が低下する。 In the formula (1), m representing the average number of moles of the oxyalkylene group added is 1 to 30, preferably 1 to 25, and more preferably 5 to 20. When m, which represents the average number of moles of oxyalkylene groups added, is less than 1, the shrinkage reducing property is lowered, and when m is larger than 30, the frost damage resistance is lowered.
本発明で示されるセメント用収縮低減剤は式（２）で示されるポリオキシアルキレン誘導体（成分（Ｂ））を有効成分として含む。
Ｒ３Ｏ−（ＰＯ）ｎ−Ｈ ・・・（２）
The shrinkage reducing agent for cement represented by the present invention contains a polyoxyalkylene derivative (component (B)) represented by the formula (2) as an active ingredient.
R 3 O- (PO) n- H ... (2)
式（２）において、Ｒ３は、炭素数１〜２２の炭化水素基から選ばれる一種または二種以上である。Ｒ３は、好ましくは炭素数１〜１４の炭化水素基であり、より好ましくは炭素数１〜６の炭化水素基であり、特に好ましくは炭素数２〜５の炭化水素基である。Ｒ３としては、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、イソステアリル基、イコシル基、ドコシル基が挙げられる。炭素数１〜６の炭化水素基としては、直鎖でも分岐でも良いが、直鎖のものがより好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基などが挙げられる。
In the formula (2), R 3 is one or more selected from hydrocarbon groups having 1 to 22 carbon atoms. R 3 is preferably a hydrocarbon group having 1 to 14 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 2 to 5 carbon atoms. The R 3, for example a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, isocetyl group , Octadecyl group, isostearyl group, icosyl group, docosyl group. The hydrocarbon group having 1 to 6 carbon atoms may be a linear group or a branched group, but a linear group is more preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group.
ＰＯは炭素数３のオキシアルキレン基である。また、ｎはオキシアルキレン基の平均付加モル数を表す。ｎが小さくなるにつれて作業性の改善が不十分であるため、ｎは３５以上であり、４０以上であることがより好ましく、５０以上が特に好ましい。また、ｎが大きくなるにつれて粘度が上昇し、取扱いが困難になることから、ｎは１５０以下であることが好ましく、１２０以下であることがより好ましい。
PO is an oxyalkylene group having 3 carbon atoms. Further, n represents the average number of moles of the oxyalkylene group added. Since the improvement of workability is insufficient as n becomes smaller, n is 35 or more, more preferably 40 or more, and particularly preferably 50 or more. Further, as n increases, the viscosity increases and handling becomes difficult. Therefore, n is preferably 150 or less, and more preferably 120 or less.
本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（成分（Ｂ））は、ゲル浸透クロマトグラフィー（ＧＰＣ）において、示差屈折率計を用いて得られたクロマトグラムによって規定される。このクロマトグラムとは、屈折率強度と溶出時間との関係を表すグラフである。本発明のポリオキシアルキレン誘導体では、クロマトグラムが左右非対称であり、式（３）の関係を満たす。なお、ＭＬ／ＭＨが１に近い値であるほど、クロマトグラムの形状は左右対称となる。
０．３５≦ＭＬ／ＭＨ≦０．７５ ・・・（３）
The polyoxyalkylene derivative (component (B)) contained in the shrinkage reducing agent for cement shown in the present invention is defined by a chromatogram obtained by using a differential refractometer in gel permeation chromatography (GPC). .. This chromatogram is a graph showing the relationship between the refractive index intensity and the elution time. In the polyoxyalkylene derivative of the present invention, the chromatogram is asymmetrical and satisfies the relationship of the formula (3). The closer the ML / MH is to 1, the more symmetrical the shape of the chromatogram is.
0.35 ≦ M L / M H ≦ 0.75 ··· (3)
ＭＬ／ＭＨは、それぞれ以下のようにしてクロマトグラムから算出する（図１参照）。
（１）クロマトグラム上の屈折率強度の極大点ＫからベースラインＢへ垂線を引き、垂線の長さをＬとする。
（２）屈折率強度がＬ／２となるクロマトグラム上の２点のうち、溶出時間が早いほうを点Ｏとし、溶出時間が遅いほうを点Ｑとする。
（３）点Ｏと点Ｑを結んだ直線Ｇと、屈折率強度の極大点Ｋから、ベースラインＢへ引いた垂線との交点をＰとする。
（４）点Ｏと交点Ｐの距離をＭＨ、交点Ｐと点Ｑの距離をＭＬとする。
M L / M H respectively as follows calculated from the chromatogram (see Figure 1).
(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and the length of the perpendicular line is L.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 2, the one with the earlier elution time is designated as point O, and the one with the slower dissolution time is designated as point Q.
(3) Let P be the intersection of the straight line G connecting the points O and Q and the perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) point O and the intersection point P distance M H of the distance of an intersection P and the point Q and M L.
なお、本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（成分（Ｂ））のゲル浸透クロマトグラフィーにおいて、クロマトグラムの屈折率強度の極大点が複数ある場合は、それらのうち屈折率強度が最も大きい点を極大点Ｋとする。さらに、同じ屈折率強度の極大点が複数ある場合は、溶出時間の遅いほうを屈折率強度の極大点Ｋとする。この際、ゲル浸透クロマトグラフィーに使用した展開溶媒などに起因するピークや、使用したカラムや装置に起因するベースラインの揺らぎによる擬似ピークは除く。 In the gel permeation chromatography of the polyoxyalkylene derivative (component (B)) contained in the shrinkage reducing agent for cement shown in the present invention, if there are a plurality of maximum points of the refractive index intensity of the chromatogram, among them, The point having the highest refractive index intensity is defined as the maximum point K. Further, when there are a plurality of maximum points having the same refractive index intensity, the one with the slower elution time is designated as the maximum point K of the refractive index intensity. At this time, peaks caused by the developing solvent used for gel permeation chromatography and pseudo peaks caused by baseline fluctuations caused by the columns and devices used are excluded.
本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（成分（Ｂ））は、０．３５≦ＭＬ／ＭＨ≦０．７５を満たすものである。ＭＬ／ＭＨが０．７５より大きくなると、セメント組成物の粘性が高く作業性が低下する。そのため、ＭＬ／ＭＨを０．７５以下とするが、０．６２以下とすることがより好ましく、０．５５以下が特に好ましい。
また、ＭＬ／ＭＨが０．３５より小さくなると、分子量分布における高分子量側の偏りが大きくなり、粘度が高くなり、取扱いが困難になる。そのため、ＭＬ／ＭＨを０．３５以上とするが、０．３６以上とすることがより好ましい。
Polyoxyalkylene derivative contained in cement shrinkage reducing agent represented by the present invention (component (B)) are those satisfying 0.35 ≦ M L / M H ≦ 0.75. When M L / M H is greater than 0.75, the viscosity of the cement composition has high workability is lowered. Therefore, although the 0.75 or less M L / M H, more preferably to 0.62 or less, particularly preferably 0.55 or less.
Further, when M L / M H is less than 0.35, deviation of the high molecular weight side is increased in the molecular weight distribution, the viscosity becomes high, the handling becomes difficult. Therefore, although the a M L / M H 0.35 or more, and more preferably set to 0.36 or more.
本発明において、ＭＬおよびＭＨを求めるためのゲル浸透クロマトグラフィー（ＧＰＣ）は、システムとしてＳＨＯＤＥＸ ＧＰＣ１０１専用システム、示差屈折率計としてＳＨＯＤＥＸ ＲＩ−７１Ｓ、ガードカラムとしてＳＨＯＤＥＸ ＫＦ−ＧＳ、カラムとしてＳＨＯＤＥＸ ＫＦ８０４Ｌを３本連続装着し、カラム温度４０℃、展開溶媒としてテトラヒドロフランを１ｍｌ／分の流速で流し、得られた反応物の０．１質量部のテトラヒドロフラン溶液０．１ｍｌを注入し、ＢＲＯＷＩＮ ＧＰＣ計算プログラムを用いて屈折率強度と溶出時間で表されるクロマトグラムを得る。 In the present invention, gel permeation chromatography (GPC) for determining ML and MH is a system dedicated to SHODEX GPC101, a differential refractometer SHODEX RI-71S, a guard column SHODEX KF-GS, and a column SHODEX. Three KF804Ls were continuously mounted, a column temperature of 40 ° C., tetrahydrofuran was flowed as a developing solvent at a flow rate of 1 ml / min, and 0.1 ml of a tetrahydrofuran solution of 0.1 parts by mass of the obtained reaction product was injected to calculate BROWIN GPC. The program is used to obtain chromatograms expressed in refractive refractometer intensity and elution time.
本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（成分（Ｂ））を製造する際には、好ましくは、複合金属シアン化物触媒（以下、ＤＭＣ触媒と略記する）の存在下で、炭素数３のプロピレンオキシドを開環付加させる。反応容器内に、分子中に少なくとも１個の水酸基を有する原料アルコールとＤＭＣ触媒を加え、不活性ガス雰囲気の撹拌下、プロピレンオキシドを連続もしくは断続的に添加し付加重合する。ポリオキシプロピレンは加圧して添加しても良く、大気圧下で添加しても良い。 When producing the polyoxyalkylene derivative (component (B)) contained in the shrinkage reducing agent for cement shown in the present invention, it is preferable in the presence of a composite metal cyanide catalyst (hereinafter abbreviated as DMC catalyst). Then, propylene oxide having 3 carbon atoms is ring-opened and added. A raw material alcohol having at least one hydroxyl group in the molecule and a DMC catalyst are added to the reaction vessel, and propylene oxide is continuously or intermittently added under stirring in an inert gas atmosphere for addition polymerization. Polyoxypropylene may be added under pressure, or may be added under atmospheric pressure.
この時、プロピレンオキシドの平均供給速度に制限はないが、プロピレンオキシドの仕込み量によって変化させることが望ましい。具体的には、プロピレンオキシドの全供給量の５〜２０質量部を供給する間の速度をＶ１、プロピレンオキシドの全供給量の２０〜５０質量部を供給する間の速度をＶ２、プロピレンオキシドの全供給量の５０〜１００質量部を供給する間の速度をＶ３とした時、Ｖ１／Ｖ２＝１．１〜２．０、Ｖ２／Ｖ３＝１．１〜１．５となるようにプロピレンオキシドの平均供給速度を制御することが好ましい。
また、反応温度は、５０〜１５０℃が好ましく、７０〜１１０℃がより好ましい。反応温度が１５０℃より高いと、触媒が失活するおそれがあり、反応温度が５０℃より低いと、反応速度が遅く生産性に劣る。
At this time, the average supply rate of propylene oxide is not limited, but it is desirable to change it depending on the amount of propylene oxide charged. Specifically, the rate between supplying 5 to 20 parts by mass of the total supply of propylene oxide is V 1 , and the rate between supplying 20 to 50 parts by mass of the total supply of propylene oxide is V 2 , propylene. When the velocity between supplying 50 to 100 parts by mass of the total amount of oxide supplied is V 3 , V 1 / V 2 = 1.1 to 2.0, V 2 / V 3 = 1.1 to 1. It is preferable to control the average supply rate of propylene oxide so as to be 5.
The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 110 ° C. If the reaction temperature is higher than 150 ° C, the catalyst may be deactivated, and if the reaction temperature is lower than 50 ° C, the reaction rate is slow and the productivity is poor.
本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（成分（Ｂ））を製造する際には、原料アルコールとして、式（２）においてＲ３で示される炭素数１〜２２の炭化水素を有する１価アルコールを使用することができる。 In preparing the polyoxyalkylene derivatives contained in cement shrinkage reducing agent represented by the present invention (component (B)), when using an alcohol of the formula (2) in 1 to 22 carbon atoms represented by R 3 A monohydric alcohol having a hydrocarbon can be used.
原料アルコールおよびプロピレンオキシドに含まれる微量の水分量については特に制限はないが、原料アルコールに含まれる水分量については０．５質量部以下、プロピレンオキシドに含まれる水分量については０．１質量部以下であることが望ましい。 The amount of water contained in the raw material alcohol and propylene oxide is not particularly limited, but the amount of water contained in the raw material alcohol is 0.5 parts by mass or less, and the amount of water contained in propylene oxide is 0.1 part by mass. It is desirable that it is as follows.
ＤＭＣ触媒の使用量は、特に制限されるものではないが、生成するポリオキシアルキレン誘導体に対して０．０００１〜０．１質量部が好ましく、０．００１〜０．０５質量部がより好ましい。ＤＭＣ触媒の反応系への投入は初めに一括して導入しても良く、順次分割して導入しても良い。反応終了後、複合金属錯体触媒の除去を行う。触媒の除去は、濾別や遠心分離、合成吸着剤による処理など公知の方法により行うことができる。 The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 parts by mass, more preferably 0.001 to 0.05 parts by mass with respect to the polyoxyalkylene derivative to be produced. The DMC catalyst may be introduced into the reaction system all at once at the beginning, or may be introduced separately in sequence. After completion of the reaction, the composite metal complex catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.
本発明で示されるセメント用収縮低減剤に含まれるポリオキシアルキレン誘導体（Ｂ）を製造する際に用いるＤＭＣ触媒は公知のものを用いることができ、例えば式（４）で表すことができる。
Ｍａ[Ｍ’ｘ（ＣＮ）ｙ]ｂ(Ｈ２Ｏ)ｃ・（Ｒ）d ・・・（４）
A known DMC catalyst can be used for producing the polyoxyalkylene derivative (B) contained in the shrinkage reducing agent for cement shown in the present invention, and can be represented by, for example, the formula (4).
Ma [M'x (CN) y] b (H 2 O) c · (R) d ··· (4)
式（４）中、ＭおよびＭ’は金属、Ｒは有機配位子、a、ｂ、ｘおよびｙは金属の原子価と配位数により変わる正の整数であり、ｃおよびｄは、金属の配位数により変わる正の整数である。 In formula (4), M and M'are metals, R is an organic ligand, a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and c and d are metals. It is a positive integer that changes depending on the coordination number of.
金属Ｍとしては、Ｚｎ（II）、Ｆｅ（II）、Ｆｅ（III）、Ｃｏ（II）、Ｎｉ（II）、Ａｌ（III）、Ｓｒ（II）、Ｍｎ（II）、Ｃｒ（III）、Ｃｕ（II）、Ｓｎ（II）、Ｐｂ（II）、Ｍｏ（IV）、Ｍｏ（VI）、Ｗ（IV）、Ｗ（VI）などが挙げられ、なかでもＺｎ（II）が好ましく用いられる。 Examples of the metal M include Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Examples thereof include Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), and Zn (II) is preferably used.
金属Ｍ’としては、Ｆｅ（II）、Ｆｅ（III）、Ｃｏ（II）、Ｃｏ（III）、Ｃｒ（II）、Ｃｒ（III）、Ｍｎ（II）、Ｍｎ（III）、Ｎｉ（II）、Ｖ（IV）、Ｖ（V）などがあげられ、なかでもＦｅ（II）、Ｆｅ（III）、Ｃｏ（II）、Ｃｏ（III）が好ましく用いられる。 Examples of the metal M'are Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II). , V (IV), V (V) and the like, and among them, Fe (II), Fe (III), Co (II) and Co (III) are preferably used.
有機配位子としてはアルコール、エーテル、ケトン、エステルなどが使用でき、アルコールがより好ましい。好ましい有機配位子は水溶性のものであり、具体例としては、tert-ブチルアルコール、ｎ−ブチルアルコール、iso-ブチルアルコール、Ｎ,N-ジメチルアセトアミド、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどが挙げられる。特に好ましくはtert-ブチルアルコールが配位したＺｎ３[Ｃｏ（ＣＮ）６]２である。 As the organic ligand, alcohol, ether, ketone, ester and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. .. Particularly preferably, it is Zn 3 [Co (CN) 6 ] 2 coordinated with tert-butyl alcohol.
本発明で示されるセメント用収縮低減剤は、成分（Ａ）：成分（Ｂ）が９０．０〜９９．９質量部：１０．０〜０．１質量部であり、好ましくは９３．０〜９９．０質量部：７．０〜１．０質量部であり、より好ましくは９３．０〜９７．０質量部：７．０〜３．０質量部である。成分（Ｂ）の比率が０．１質量部未満である場合、セメント組成物の粘性が高くなり作業性が低下する。成分（Ｂ）の比率が１０．０質量部より多い場合、耐凍害性の低下が大きく、耐久性が低下する。 The shrinkage reducing agent for cement shown in the present invention has a component (A): component (B) of 90.0 to 99.9 parts by mass: 10.0 to 0.1 parts by mass, preferably 93.0 to 93.0 parts by mass. 99.0 parts by mass: 7.0 to 1.0 parts by mass, more preferably 93.0 to 97.0 parts by mass: 7.0 to 3.0 parts by mass. When the ratio of the component (B) is less than 0.1 parts by mass, the viscosity of the cement composition becomes high and the workability is lowered. When the ratio of the component (B) is more than 10.0 parts by mass, the frost damage resistance is greatly reduced and the durability is lowered.
本発明のセメント用収縮低減剤は、セメント又はセメント組成物に添加して使用する。セメント組成物としては、モルタル、コンクリートなどが挙げられる。 The shrinkage reducing agent for cement of the present invention is used by adding it to cement or a cement composition. Examples of the cement composition include mortar and concrete.
本発明のセメント用収縮低減剤を適用することができるセメントとしては、普通、早強、超早強、低熱、中庸熱、耐硫酸塩等のポルトランドセメントや、これらポルトランドセメントに、高炉スラグ、フライアッシュ、又はシリカを混合した各種混合セメント、エコセメント、白色セメント、超速硬セメントなどが挙げられる。 Examples of cement to which the shrinkage reducing agent for cement of the present invention can be applied include Portland cements such as ordinary, early-strength, ultra-fast-strength, low-heat, moderate-heat, and sulfate-resistant, and blast furnace slag and fly to these Portland cements. Examples thereof include various mixed cements mixed with ash or silica, eco-cement, white cement, and ultrafast hard cement.
本発明のセメント用収縮低減剤を適用することができる骨材としては、通常のモルタルやコンクリートに使用できるものであれば特に限定されるものではなく、川砂、山砂、陸砂、砕砂、けい砂等の細骨材や、川砂利、山砂利、陸砂利、砕石、人工軽量骨材、高炉スラグ砕石および再生骨材等の粗骨材が挙げられる。 The aggregate to which the shrinkage reducing agent for cement of the present invention can be applied is not particularly limited as long as it can be used for ordinary mortar or concrete, and river sand, mountain sand, land sand, crushed sand, and gravel. Examples include fine aggregates such as sand and coarse aggregates such as river gravel, mountain gravel, land gravel, crushed stone, artificial lightweight aggregate, blast furnace slag crushed stone and recycled aggregate.
本発明のセメント用収縮低減剤の使用量は、特に限定されないが、セメント、モルタル又はコンクリート等に添加するに際し、セメント１００質量部に対し０．１〜１０質量部であり、好ましくは０．５〜８質量部であり、より好ましくは１〜６質量部である。 The amount of the shrinkage reducing agent for cement of the present invention used is not particularly limited, but is 0.1 to 10 parts by mass, preferably 0.5 parts by mass, based on 100 parts by mass of cement when added to cement, mortar, concrete, or the like. It is ~ 8 parts by mass, more preferably 1 to 6 parts by mass.
本発明のセメント用収縮低減剤の使用方法は、特に限定されない。セメント用収縮低減剤を注水と同時に添加して使用することができ、注水から練り上がりまでの間に添加して使用することができ、一旦練り上がったセメント組成物に添加して使用することもできる。 The method of using the shrinkage reducing agent for cement of the present invention is not particularly limited. A shrinkage reducing agent for cement can be added and used at the same time as water injection, can be added and used between water injection and kneading, and can also be added and used in a cement composition once kneaded. it can.
本発明のセメント用収縮低減剤は、その効果を阻害しない範囲で、他の添加剤（添加材）と併用することができる。他の添加剤としては、減水剤、ＡＥ剤、ＡＥ減水剤、収縮低減剤、消泡剤、空気量調整剤、凝結遅延剤、凝結促進剤、膨張材、流動化剤、起泡剤、分離抑制剤、保水剤、増粘剤、防水剤等が挙げられる。 The shrinkage reducing agent for cement of the present invention can be used in combination with other additives (additives) as long as the effect is not impaired. Other additives include water reducing agents, AE agents, AE water reducing agents, shrinkage reducing agents, defoaming agents, air volume adjusting agents, coagulation retarders, coagulation accelerators, swelling agents, fluidizing agents, foaming agents, and separation. Inhibitors, water retention agents, thickeners, waterproof agents and the like can be mentioned.
本発明では、セメント組成物の調製に使用する水の量は、配合用途に応じて定めることができるが、通常、セメント１００質量部に対して１０〜７０質量部であり、より好ましくは１０〜６０質量部であり、さらに好ましくは２０〜５５質量部である。 In the present invention, the amount of water used for preparing the cement composition can be determined according to the compounding use, but is usually 10 to 70 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of cement. It is 60 parts by mass, more preferably 20 to 55 parts by mass.
以下に、実施例を挙げて本発明を説明する。
（ポリオキシアルキレン化合物：成分（Ａ−１）の合成例）
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイルおよび蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、ステアリルアルコールを主成分とする原料（ステアリルアルコール含有率：約９０質量％、セチルアルコール含有率：約１０質量％）５３５ｇ（２．０モル）と、触媒としてソジウムメチラートを量り取り、系内を窒素ガスで置換した。撹拌下、１００〜１２０℃、０．０５〜０．５０MPa（ゲージ圧）の条件で、ガス吹き込み管よりプロピレンオキシド１１６０ｇ（２０モル）を徐々に圧入した。添加終了後、同条件で内圧が一定となるまで反応させた後、窒素ガスを吹き込みながら１３kPa以下、８０℃で１時間減圧処理を行った。窒素ガスで０．０５MPaまで加圧後、反応物を抜き取り、塩酸で中和し、水や副生した塩を取り除き、式（１）で表される成分（Ａ−１）を得た。
Hereinafter, the present invention will be described with reference to examples.
(Polyoxyalkylene compound: Synthesis example of component (A-1))
A 5L stainless steel high-pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blow pipe, exhaust pipe, cooling coil and steam jacket, and a raw material containing stearyl alcohol as the main component (stearyl alcohol content: About 90% by mass, cetyl alcohol content: about 10% by mass) 535 g (2.0 mol) and sodium methylate were weighed as a catalyst, and the inside of the system was replaced with nitrogen gas. Under stirring conditions, 1160 g (20 mol) of propylene oxide was gradually press-fitted from a gas blowing pipe under the conditions of 100 to 120 ° C. and 0.05 to 0.50 MPa (gauge pressure). After completion of the addition, the reaction was carried out under the same conditions until the internal pressure became constant, and then a reduced pressure treatment was carried out at 13 kPa or less and 80 ° C. for 1 hour while blowing nitrogen gas. After pressurizing to 0.05 MPa with nitrogen gas, the reaction product was extracted, neutralized with hydrochloric acid, and water and by-produced salts were removed to obtain a component (A-1) represented by the formula (1).
（成分（Ａ−２）の合成例）
プロピレンオキシド１７４０ｇを使用した以外は、実施例１と同様にして、式（１）で表される成分（Ａ−２）を得た。
(Example of synthesis of component (A-2))
A component (A-2) represented by the formula (1) was obtained in the same manner as in Example 1 except that 1740 g of propylene oxide was used.
（成分（Ａ−３）の合成例）
ラウリルアルコールを主成分とする原料（ラウリルアルコール含有率：約９５質量％、ミリスチルアルコール含有率：約５質量％）３７２ｇ（２．０モル）とプロピレンオキシド１１６０ｇ（２０モル）を使用した以外は、実施例１と同様にして、式（１）で表される成分（Ａ−３）を得た。
(Example of synthesis of component (A-3))
Except for using 372 g (2.0 mol) and 1160 g (20 mol) of propylene oxide as raw materials containing lauryl alcohol as a main component (lauryl alcohol content: about 95% by mass, myristyl alcohol content: about 5% by mass). In the same manner as in Example 1, a component (A-3) represented by the formula (1) was obtained.
（成分（Ａ−４）の合成例）
原料としてｎ−ブタノール１４８ｇを使用し、プロピレンオキシド１１６０ｇを使用した以外は、実施例１と同様にして、式（１）で表される成分（Ａ−４）を得た。
(Example of synthesis of component (A-4))
A component (A-4) represented by the formula (1) was obtained in the same manner as in Example 1 except that 148 g of n-butanol was used as a raw material and 1160 g of propylene oxide was used.
（成分（Ａ’−１）の合成例）
原料としてメタノール１６０ｇ（５モル）を使用し、エチレンオキシド４４０ｇ（１０モル）、プロピレンオキシド５８０ｇ（１０モル）を使用した以外は、実施例１と同様にして合成し、本発明外の成分（Ａ’−１）を得た。
(Example of synthesis of component (A'-1))
Synthesis was carried out in the same manner as in Example 1 except that 160 g (5 mol) of methanol was used as a raw material, 440 g (10 mol) of ethylene oxide and 580 g (10 mol) of propylene oxide were used, and a component (A') other than the present invention was used. -1) was obtained.
（成分（Ａ’−２）の合成例）
エチレンオキシド８８０ｇ（２０モル）を使用した以外は、実施例１と同様にして合成し、本発明外の成分（Ａ’−２）を得た。
(Example of synthesis of component (A'-2))
Synthesis was carried out in the same manner as in Example 1 except that 880 g (20 mol) of ethylene oxide was used to obtain a component (A'-2) outside the present invention.
（複合金属シアン化物錯体触媒の合成）
塩化亜鉛２．１ｇを含む２．０ｍｌの水溶液中に、カリウムヘキサシアノコバルテートＫ３Ｃｏ（ＣＮ）６を０．８４ｇ含む１５ｍｌの水溶液を、４０℃にて撹拌しながら１５分間かけて滴下した。滴下終了後、水１６ｍｌ、tert-ブチルアルコール１６ｇを加え、７０℃に昇温し、１時間撹拌した。室温まで冷却後、濾過操作を行い、固体を得た。この固体に、水１４ｍｌ、tert-ブチルアルコール８．０ｇを加え、３０分間撹拌した後、濾過操作を行い、固体を得た。さらに再度、この固体にtert-ブチルアルコール１８．６ｇ、メタノール１．２ｇを加え、３０分間撹拌した後、濾過操作を行い、得られた固体を４０℃、減圧下で３時間乾燥し、複合金属シアン化物錯体触媒０．７ｇを得た。
(Synthesis of composite metal cyanide complex catalyst)
In an aqueous solution of 2.0ml containing zinc chloride 2.1 g, an aqueous solution of potassium hexacyanocobaltate K 3 Co (CN) 6 and comprises 0.84 g 15 ml, was added dropwise with stirring over 15 minutes at 40 ° C.. After completion of the dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and the mixture was stirred for 30 minutes and then filtered to obtain a solid. Further, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid again, and the mixture was stirred for 30 minutes and then filtered. The obtained solid was dried at 40 ° C. under reduced pressure for 3 hours to obtain a composite metal. 0.7 g of cyanide complex catalyst was obtained.
（ポリオキシアルキレン化合物：成分（Ｂ）の合成）
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイルおよび蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、ｎ−ブタノール２００ｇと、上記した合成例の複合金属シアン化物錯体触媒０．２ｇを量り取り、系内を窒素ガスで置換した。撹拌下、１００〜１２０℃、０．０５〜０．３０MPa以下の条件で、ガス吹き込み管より、プロピレンオキシド２４３ｇを１６時間かけて滴下した。その後、反応槽内を１００〜１２０℃に保ちながら、撹拌下、０．０５〜０．６０MPaの条件で、ガス吹き込み管より、徐々にプロピレンオキシドを投入し、全量で３２７０ｇを加圧添加した。添加終了後、１００〜１２０℃で１時間反応させた。反応槽から２２００ｇを抜き取り、反応槽内の残存物を１００〜１２０℃に昇温し、０．０５〜０．６０MPaの条件で、ガス吹き込み管より、プロピレンオキシド１１１０ｇを２時間かけて添加した。添加終了後、１００〜１２０℃で１時間反応させた。再度、反応槽より１０４４ｇを抜き取り、反応槽の残存物を１１０℃へと昇温し、０．０５〜０．６０MPaの条件で、ガス吹き込み管より、プロピレンオキシド３１２ｇを４０分かけて添加した。添加終了後、１００〜１２０℃で１時間反応させた後、窒素ガスを吹き込みながら１３kPa以下、８０℃で１時間減圧処理を行った。窒素ガスで０．０５MPaまで加圧後、反応物を抜き取り、濾過を行い、表２の成分（Ｂ−１）を得た。
(Polyoxyalkylene compound: Synthesis of component (B))
In a stainless steel 5L high pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blow pipe, exhaust pipe, cooling coil and steam jacket, 200 g of n-butanol and the composite metal cyanide of the above synthetic example 0.2 g of the compound complex catalyst was weighed, and the inside of the system was replaced with nitrogen gas. Under stirring conditions, 243 g of propylene oxide was added dropwise from a gas blowing tube under the conditions of 100 to 120 ° C. and 0.05 to 0.30 MPa or less over 16 hours. Then, while keeping the inside of the reaction vessel at 100 to 120 ° C., propylene oxide was gradually added from the gas blowing tube under the condition of 0.05 to 0.60 MPa under stirring, and 3270 g in total was added under pressure. After completion of the addition, the reaction was carried out at 100 to 120 ° C. for 1 hour. 2200 g was withdrawn from the reaction vessel, the temperature of the residue in the reaction vessel was raised to 100 to 120 ° C., and 1110 g of propylene oxide was added from a gas blowing tube under the condition of 0.05 to 0.60 MPa over 2 hours. After completion of the addition, the reaction was carried out at 100 to 120 ° C. for 1 hour. Again, 1044 g was withdrawn from the reaction vessel, the residue in the reaction vessel was heated to 110 ° C., and 312 g of propylene oxide was added from a gas blowing tube under the condition of 0.05 to 0.60 MPa over 40 minutes. After completion of the addition, the reaction was carried out at 100 to 120 ° C. for 1 hour, and then reduced pressure treatment was carried out at 13 kPa or less and 80 ° C. for 1 hour while blowing nitrogen gas. After pressurizing to 0.05 MPa with nitrogen gas, the reaction product was extracted and filtered to obtain the component (B-1) in Table 2.
（成分（Ｂ−２）の合成例）
プロピレンオキシド全添加量を４７７９ｇとした以外は、成分（Ｂ−１）と同様にして、表２に示す成分（Ｂ−２）を得た。
(Example of synthesis of component (B-2))
The component (B-2) shown in Table 2 was obtained in the same manner as the component (B-1) except that the total amount of propylene oxide added was 4779 g.
（成分（Ｂ−３）の合成例）
プロピレンオキシド全添加量を４９０１ｇとした以外は、成分（Ｂ−１）と同様にして、表２に示す成分（Ｂ−３）を得た。
(Example of synthesis of component (B-3))
The component (B-3) shown in Table 2 was obtained in the same manner as the component (B-1) except that the total amount of propylene oxide added was 4901 g.
（成分（Ｂ’−１）の合成例）
撹拌機、圧力計、温度計、安全弁、ガス吹き込み管、排気管、冷却用コイルおよび蒸気ジャケットを装備したステンレス製５Ｌの高圧反応装置に、分子量１２９０のポリオキシプロピレンブチルエーテル２５０ｇと水酸化カリウム５．４ｇを量り取り、１００℃でプロピレンオキシド２３２２ｇを反応させた後、窒素ガスを吹き込みながら１３kPa以下、８０℃で１時間減圧処理を行った。窒素ガスで０．０５MPaまで加圧後、反応物を抜き取り、塩酸で中和し、水や副生した塩を取り除いた後に、濾過を行い、本発明外の成分（Ｂ’−１）を得た。
(Example of synthesis of component (B'-1))
2. 250 g of polyoxypropylene butyl ether having a molecular weight of 1290 and potassium hydroxide in a stainless steel 5 L high-pressure reactor equipped with a stirrer, pressure gauge, thermometer, safety valve, gas blow pipe, exhaust pipe, cooling coil and steam jacket. After weighing 4 g and reacting 2322 g of propylene oxide at 100 ° C., a reduced pressure treatment was carried out at 13 kPa or less and 80 ° C. for 1 hour while blowing nitrogen gas. After pressurizing to 0.05 MPa with nitrogen gas, the reaction product is extracted, neutralized with hydrochloric acid, water and by-produced salts are removed, and then filtered to obtain a component (B'-1) outside the present invention. It was.
得られた各成分（Ｂ−１）〜（Ｂ−３）、（Ｂ’−１）について、ゲル浸透クロマトグラフィーによる測定を行った。表２に、得られた各成分（Ｂ−１）〜（Ｂ−３）、（Ｂ’−１）の仕様と分析値を示す。なお、表２には、「ＰＲＥＭＩＮＯＬ Ｓ １００４Ｆ」（旭硝子（株）製、高分子量ポリプロピレングリコール）も示す。 Each of the obtained components (B-1) to (B-3) and (B'-1) was measured by gel permeation chromatography. Table 2 shows the specifications and analytical values of the obtained components (B-1) to (B-3) and (B'-1). Table 2 also shows "PREMINOL S 1004F" (manufactured by Asahi Glass Co., Ltd., high molecular weight polypropylene glycol).
（ゲル浸透クロマトグラフィーの測定）
ゲル浸透クロマトグラフィーには、システムとしてＳＨＯＤＥＸ ＧＰＣ１０１専用システム、示差屈折率計としてＳＨＯＤＥＸ ＲＩ−７１Ｓ、ガードカラムとしてＳＨＯＤＥＸ ＫＦ−ＧＳ、カラムとしてＳＨＯＤＥＸ ＫＦ８０４Ｌを３本連続装着し、カラム温度４０℃、展開溶媒としてテトラヒドロフランを１ｍｌ／分の流速で流し、得られた反応物の０．１質量％テトラヒドロフラン溶液０．１ｍｌを注入し、ＢＲＯＷＩＮ ＧＰＣ計算プログラムを用いて屈折率強度と溶出時間で表されるクロマトグラムを得た。このクロマトグラムからＭＬ／ＭＨを求め、表２に示す。
(Measurement of gel permeation chromatography)
For gel permeation chromatography, a dedicated system for SHODEX GPC101, a lordex RI-71S as a differential refractometer, SHODEX KF-GS as a guard column, and SHODEX KF804L as a column were continuously mounted, and the column temperature was 40 ° C. and the developing solvent was used. Tetrahydrofuran was flowed at a flow rate of 1 ml / min, 0.1 ml of a 0.1 mass% tetrahydrofuran solution of the obtained reaction product was injected, and a chromatogram represented by a refractive refractometer intensity and an elution time using a BROWIN GPC calculation program. Got ML / MH was obtained from this chromatogram and is shown in Table 2.
次いで、表３に示す割合で各成分をビーカーに量り取り、撹拌羽根を使用して１０分間撹拌を行い、各例のセメント用収縮低減剤を得た。 Next, each component was weighed in a beaker at the ratio shown in Table 3 and stirred for 10 minutes using a stirring blade to obtain a shrinkage reducing agent for cement of each example.
（モルタルの製造）
セメント１００質量部（セメント協会製）、細骨材（山砂、千葉産）２００質量部を強制練りミキサで空練り後、水５０質量部と、各例のセメント用収縮低減剤２質量部を加えて混練し、モルタルとした。単位容積質量は２，０９０±２０ｇ/Ｌ、モルタル温度は２０±２℃であった。
表３に示す各モルタルの特性を測定し、測定結果を表４、表５に示す。
(Manufacturing of mortar)
After kneading 100 parts by mass of cement (manufactured by Cement Association) and 200 parts by mass of fine aggregate (Yamasago, Chiba) with a forced kneading mixer, add 50 parts by mass of water and 2 parts by mass of shrinkage reducing agent for cement in each example. In addition, it was kneaded to make a mortar. The unit volume mass was 2,090 ± 20 g / L, and the mortar temperature was 20 ± 2 ° C.
The characteristics of each mortar shown in Table 3 were measured, and the measurement results are shown in Tables 4 and 5.
（測定方法）
＜作業性の評価＞
モルタルのスランプ値およびスランプフロー値の測定は、ＪＩＳ Ａ １１７１に記載の上端内径５０ｍｍ、下端内径１００ｍｍ、高さ１５０ｍｍのスランプコーンにモルタルを２層に分けて充填し、上面をスランプコーンの上端に合わせて均した後、直ちにスランプコーンを静かに鉛直に引き上げ、頂部の下がりをスランプ値として、モルタルの広がりが静止した時点での最大直径とそれに直交する直径を測定し、その平均値をスランプフロー値として測定した。粘性の評価は、モルタルのスランプを測定する際、スランプ値が同じでも粘性の差異によってスランプフロー値が変化するという現象をもとに行った。すなわち、モルタルスランプが同じでフローが大きくなることは、粘性が低く作業性に優れるという現象を利用し、スランプフローの（長径／２）×（短径／２）×円周率で求められるフロー面積をスランプ値で除した値で表した。この値は、粘性が低いものほど大きくなる。
(Measuring method)
<Evaluation of workability>
The slump value and slump flow value of the mortar are measured by filling a slump cone having an upper end inner diameter of 50 mm, a lower end inner diameter of 100 mm and a height of 150 mm described in JIS A 1171 in two layers, and placing the upper surface on the upper end of the slump cone. Immediately after leveling the mortar, gently pull up the slump cone vertically, measure the maximum diameter at the time when the mortar spread is stationary and the diameter perpendicular to it, and use the slump flow as the slump value. Measured as a value. The viscosity was evaluated based on the phenomenon that the slump flow value changes due to the difference in viscosity even if the slump value is the same when measuring the slump of the mortar. That is, the fact that the mortar slump is the same and the flow is large utilizes the phenomenon that the viscosity is low and the workability is excellent, and the flow obtained by the slump flow (major diameter / 2) × (minor diameter / 2) × pi is obtained. It was expressed as the value obtained by dividing the area by the slump value. This value increases as the viscosity decreases.
表４に、スランプ値、スランプフロー値、フロー面積をスランプ値で除した値を示す。フロー面積／スランプ値が大きいものほど、粘性が低く、作業性が良好であるとして評価した。 Table 4 shows the slump value, the slump flow value, and the value obtained by dividing the flow area by the slump value. The larger the flow area / slump value, the lower the viscosity and the better the workability.
＜収縮低減性の評価＞
収縮低減性の評価は、上記モルタルを４×４×１６（ｃｍ）のゲージプラグ付き金型に充填し、養生温度２０℃、材齢１日で脱型および基長の測定を行い、その後２０±２℃、湿度５５％ＲＨにて気中養生し、ＪＩＳ Ａ １１２９−３「モルタルおよびコンクリートの長さ変化試験（ダイヤルゲージ方法）」に準拠した長さ変化試験を実施し、収縮率が小さいものほど収縮低減性が高いものとして評価した。
<Evaluation of shrinkage reduction>
To evaluate the shrinkage reduction property, the above mortar was filled in a mold with a gauge plug of 4 × 4 × 16 (cm), demolded and the base length was measured at a curing temperature of 20 ° C. and a material age of 1 day, and then 20 Cured in air at ± 2 ° C and humidity 55% RH, and conducted a length change test in accordance with JIS A 1129-3 "Mortar and concrete length change test (dial gauge method)", and the shrinkage rate is small. It was evaluated as having a higher shrinkage reduction property.
＜耐凍害性の評価＞
耐凍害性の評価は、上記モルタルを１０×１０×４０（ｃｍ）の金型に充填し、養生温度２０℃、材齢２日で脱型および２０±２℃で１４日水中養生、２０±２℃で１２日気中養生後、ＪＩＳ Ａ １１４８「コンクリートの凍結融解試験方法（水中凍結融解試験方法）」に準拠し、５±２℃から−１８±２℃の温度条件で凍結融解サイクルを与え、ＪＩＳ Ａ １１２７「共鳴振動によるコンクリートの動弾性係数、動せん断弾性係数及び動ポアソン比試験方法」に準拠して測定した一次共鳴振動数から、ＪＩＳ Ａ １１４８に記載の相対動弾性係数を算出し、その値が低下しないものほど、耐凍害性が高いものとして評価した。
<Evaluation of frost damage resistance>
For the evaluation of frost damage resistance, the above mortar was filled in a mold of 10 × 10 × 40 (cm), demolded at a curing temperature of 20 ° C. and aged 2 days, and cured in water at 20 ± 2 ° C. for 14 days, 20 ±. After aerial curing at 2 ° C for 12 days, the freeze-thaw cycle is performed under temperature conditions of 5 ± 2 ° C to -18 ± 2 ° C in accordance with JIS A 1148 “Concrete freeze-thaw test method (in-water freeze-thaw test method)”. Given, the relative dynamic elasticity coefficient described in JIS A 1148 is calculated from the primary resonance frequency measured in accordance with JIS A 1127 "Dynamic elastic modulus, dynamic shear elastic coefficient and dynamic Poisson's ratio test method of concrete by resonance vibration". However, the more the value did not decrease, the higher the frost damage resistance was evaluated.
＜圧縮強度の測定＞
圧縮強度の評価は、上記モルタルを４×４×１６（ｃｍ）の金型に充填し、養生温度２０℃、材齢１日で脱型し、その後、２０±２℃で材齢２８日まで水中養生後、ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」に準拠した圧縮強度測定を実施した。
<Measurement of compression strength>
For evaluation of compressive strength, the above mortar is filled in a 4 × 4 × 16 (cm) mold, demolded at a curing temperature of 20 ° C. and a material age of 1 day, and then at 20 ± 2 ° C. until a material age of 28 days. After curing in water, the compressive strength was measured in accordance with JIS R 5201 “Physical test method for cement”.
収縮低減剤無添加（比較例１）の収縮率および相対動弾性係数をそれぞれ１００とした場合の、無添加に対する２８日収縮率および３００サイクル相対動弾性係数の割合、圧縮強度測定の結果を表５に示す。収縮率が小さいものほど収縮低減性が高く、相対動弾性係数が大きいものほど、耐凍害性が高いことを示している。 The table shows the ratio of the 28-day shrinkage coefficient and the 300-cycle relative dynamic elastic modulus to the non-addition when the shrinkage rate and the relative dynamic elastic modulus of each of the shrinkage reducing agents not added (Comparative Example 1) are 100, and the results of the compression strength measurement. Shown in 5. The smaller the shrinkage rate, the higher the shrinkage reduction property, and the larger the relative elastic modulus, the higher the frost damage resistance.
＜評価基準＞
・作業性： フロー面積／スランプ値；
２０以上：○、 ２０未満：×
・収縮低減性： 無添加に対する２８日収縮低減率；
７０未満：◎、 ７０以上９０未満：○、 ９０以上１００未満：△
・耐凍害性
： 無添加に対する２８日相対動弾性係数；
６０以上：○、 ６０未満：×
・圧縮強度 ： 無添加に対する圧縮強度比；
９０％以上： ○、９０％未満：×
<Evaluation criteria>
・ Workability: Flow area / slump value;
20 or more: ○, less than 20: ×
-Shrinkage reduction: 28-day shrinkage reduction rate with respect to no addition;
Less than 70: ◎, 70 or more and less than 90: ○, 90 or more and less than 100: △
・ Freezing damage resistance
: 28-day relative modulus for no addition;
60 or more: ○, less than 60: ×
-Compression strength: Compression strength ratio to no additives;
90% or more: ○, less than 90%: ×
実施例１〜６と比較例１〜５の比較により、本発明のセメント用収縮低減剤を添加したセメント組成物は、収縮率が小さく、耐凍害性および圧縮強度の低下が小さく、かつ粘性が低く作業性に優れていることがわかる。 By comparing Examples 1 to 6 and Comparative Examples 1 to 5, the cement composition to which the shrinkage reducing agent for cement of the present invention was added has a small shrinkage rate, a small decrease in frost damage resistance and compressive strength, and a viscosity. It can be seen that it is low and excellent in workability.
比較例１は、収縮低減剤無添加であり、耐凍害性は高いが、収縮低減効果は低く、乾燥ひび割れの抑制効果が低いことがわかる。
比較例２、３は、成分（Ｂ）のＧＰＣチャートより算出したＭＬ／ＭＨが本発明の範囲を外れており、圧縮強度の低下が大きく、フロー面積／スランプ値が小さく、粘性が高いため、作業性が低いことがわかる。
In Comparative Example 1, it can be seen that the shrinkage reducing agent is not added and the frost damage resistance is high, but the shrinkage reducing effect is low and the drying crack suppressing effect is low.
In Comparative Examples 2 and 3, the ML / MH calculated from the GPC chart of the component (B) is out of the range of the present invention, the decrease in compression strength is large, the flow area / slump value is small, and the viscosity is high. Therefore, it can be seen that the workability is low.
比較例４は、成分（Ａ）が低級アルコールアルキレンオキシド付加物であり、収縮低減効果は高いが、耐凍害性の低下が大きく、圧縮強度の低下が大きいため、耐久性が低いことがわかる。
比較例５は、ＡＯのアルキレンオキシド炭素数が本発明の範囲を外れるため、耐凍害性の低下が大きく、圧縮強度の低下が大きいため、耐久性が低いことがわかる。
In Comparative Example 4, the component (A) is a lower alcohol alkylene oxide adduct, which has a high shrinkage reducing effect, but has a large decrease in frost damage resistance and a large decrease in compression strength, so that it can be seen that the durability is low.
In Comparative Example 5, since the alkylene oxide carbon number of AO is out of the range of the present invention, the frost damage resistance is greatly reduced, and the compression strength is greatly reduced, so that the durability is low.
Claims (2)
成分（Ａ）：
下記式（１）で表されるポリオキシアルキレン誘導体
Ｒ１Ｏ−（ＡＯ）ｍ−Ｒ２
・・・（１）
（式（１）中、
Ｒ１は炭素数１〜３０の炭化水素基であり、
Ｒ２は水素原子およびメチル基からなる群より選ばれた一種以上を表し、
ＡＯは炭素数３〜４のオキシアルキレン基であり、
ｍは前記オキシアルキレン基ＡＯの平均付加モル数であり、ｍ＝１〜３０の数を示す。）
成分（Ｂ）：
下記式（２）で表され、かつゲル浸透クロマトグラフィー測定により求められるクロマトグラムから算出されるＭＨとＭＬとが下記式（３）の関係を満足するポリオキシアルキレン誘導体
Ｒ３Ｏ−（ＰＯ）ｎ−Ｈ ・・・（２）
（式（２）中、
Ｒ３は炭素数１〜２２の炭化水素基であり、
ＰＯは炭素数３のオキシアルキレン基を表し、
ｎは３５以上の数を示す。）
０．３５≦ＭＬ／ＭＨ≦０．７５ ・・・（３）
（式（３）中、
前記クロマトグラム上の屈折率強度が最大となる極大点ＫからベースラインＢへの垂線の長さをＬとし、屈折率強度がＬ／２となるクロマトグラム上の２点のうち溶出時間が早いほうを点Ｏとし、溶出時間が遅いほうを点Ｑとし、点Ｏと点Ｑを結ぶ直線Ｇと前記極大点Ｋから前記ベースラインへ引いた垂線との交点をＰとしたとき、点Ｏと交点Ｐの距離をＭＨとし、点Ｑと交点Ｐの距離をＭＬとする。）
A shrinkage reducing agent for cement, which comprises the following component (A) and component (B) in a ratio of 90.0 to 99.9 parts by mass: 10.0 to 0.1 parts by mass.
Ingredient (A):
Polyoxyalkylene derivative represented by the following formula (1)
R 1 O- (AO) m- R 2
... (1)
(In equation (1),
R 1 is a hydrocarbon group having 1 to 30 carbon atoms.
R 2 represents one or more selected from the group consisting of hydrogen atom and methyl group.
AO is an oxyalkylene group having 3 to 4 carbon atoms.
m is the average number of moles of the oxyalkylene group AO added, and indicates the number of m = 1 to 30. )
Ingredient (B):
Represented by the following formula (2), and a polyoxyalkylene derivative and a M H and M L satisfy the relation of the following formula (3) calculated from the chromatogram obtained by the gel permeation chromatography measurement
R 3 O- (PO) n- H ... (2)
(In equation (2),
R 3 is a hydrocarbon group having 1 to 22 carbon atoms.
PO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 35 or more. )
0.35 ≦ M L / M H ≦ 0.75 ··· (3)
(In equation (3),
The length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L, and the dissolution time is the fastest among the two points on the chromatogram where the refractive index intensity is L / 2. When the point O is defined as the point O, the one with the slower dissolution time is defined as the point Q, and the intersection of the straight line G connecting the point O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is P, the point O and the distance of the intersection point P and M H, the distance between the point Q and the point of intersection P and M L. )
A cement composition comprising 0.1 to 10 parts by mass of the shrinkage reducing agent for cement according to claim 1 with respect to 100 parts by mass of cement.
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| JPS59128240A (en) * | 1983-01-13 | 1984-07-24 | 日本セメント株式会社 | Shrinkage decreasing agent effective for cement |
| JP2825855B2 (en) * | 1988-07-15 | 1998-11-18 | 株式会社竹中工務店 | Cement hydraulics durability improving agent, durability improving method, and cement hydraulics with improved durability |
| JP3296332B2 (en) * | 1998-06-17 | 2002-06-24 | 日本油脂株式会社 | Polyoxyalkylene monoalkyl ether, method for producing the same, polymerizable polyoxyalkylene monoalkyl ether derivative, copolymer of the derivative, and dispersant containing the copolymer |
| JP4385440B2 (en) * | 1999-06-08 | 2009-12-16 | 日油株式会社 | Polymerizable polyoxyalkylene monoalkyl ether derivative, polymer of the derivative, and dispersant containing the polymer |
| CA2363087C (en) * | 1999-12-16 | 2012-02-14 | Sanyo Chemical Industries, Ltd. | A cement additive, a concrete composition and a structure using the same |
| JP2003171155A (en) * | 2001-12-03 | 2003-06-17 | Lion Corp | Drying shrinkage-reducing agent for cement |
| JP4459912B2 (en) * | 2006-02-10 | 2010-04-28 | 電気化学工業株式会社 | Drying shrinkage reducing agent and hardened cement using the same |
| JP2010006682A (en) * | 2008-06-30 | 2010-01-14 | Sanyo Chem Ind Ltd | Additive for cement, and cement composition |
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