JPH0637317B2 - Durability improver for freeze-thaw cement cement - Google Patents
Durability improver for freeze-thaw cement cementInfo
- Publication number
- JPH0637317B2 JPH0637317B2 JP8933886A JP8933886A JPH0637317B2 JP H0637317 B2 JPH0637317 B2 JP H0637317B2 JP 8933886 A JP8933886 A JP 8933886A JP 8933886 A JP8933886 A JP 8933886A JP H0637317 B2 JPH0637317 B2 JP H0637317B2
- Authority
- JP
- Japan
- Prior art keywords
- cement
- freeze
- thaw
- formula
- test
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004568 cement Substances 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000004567 concrete Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 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 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 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 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 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 1
- 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 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 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 1
- 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 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
【発明の詳細な説明】 産業上の利用分野： この発明はセメント水硬物の凍結融解に対する新規な耐
久性改善剤に関するものであり、さらに詳細には一般式
（Ｉ）： ［式中、Ｒ1およびＲ2はそれぞれ水素またはアルキル基
を、Ｘは式-CH2CH2O-で示される基を、Ｙは式-CH2CH(CH
3)O-で示される基または式-CH(CH3)CH2O-で示される基
を、ｍは０または１〜４の整数、ｎは１以上の整数であ
って、かつｍ＋ｎが１〜30の整数をそれぞれ意味し、Ｘ
およびＹは任意の順序で結合しているものとする］で示
される化合物の１種または２種以上を含むセメント水硬
物の凍結融解に対する耐久性改善剤に関するものであ
る。TECHNICAL FIELD The present invention relates to a novel durability improver for freeze-thaw of cement hydraulic material, and more specifically to a compound represented by the general formula (I): [Wherein R 1 and R 2 are each a hydrogen atom or an alkyl group, X is a group represented by the formula —CH 2 CH 2 O—, and Y is a group represented by the formula —CH 2 CH (CH
Group or the formula -CH (CH 3) CH 2 O- a group represented indicated by 3) O-, m is 0 or an integer from 1 to 4, n represents an integer of 1 or more, is and m + n 1 Each means an integer of ~ 30, X
And Y are bonded in any order]] to a freeze-thaw durability improver for cement hydraulic cements containing one or more compounds represented by the formula [1].
従来の技術： コンクリート、モルタル等のセメント水硬物が気象作用
をうける場合、寒暖のくり返しにより凍結および融解を
くり返すことになり、その結果コンクリート、モルタル
等のセメント水硬物の内部組織に微細なひびわれが発生
し、そのひびわれが大きくなるセメント水硬物の崩壊に
至る。Conventional technology: When cement hydraulic materials such as concrete and mortar are subjected to meteorological action, they are repeatedly frozen and thawed by repeated cold and heat, and as a result, the internal structure of the cement hydraulic materials such as concrete and mortar becomes fine. Cracks occur, leading to the collapse of the cement hydraulic material, where the cracks increase.
従来からこのような凍結融解作用によるセメント水硬物
の耐久性を損うのを防ぐため、空気連行剤（AE剤）が使
用されており、これによりセメント水硬物中に微細な空
気泡を連行させ、その空気泡によって凍結時の膨張圧を
緩和、吸収させることが広く行われている［例えば、
「コンクリート工学ハンドブック」（株式会社朝倉書店
発行、1981年版）、第139-143頁］。Conventionally, an air entraining agent (AE agent) has been used to prevent the deterioration of the durability of cement hydraulic products due to such freezing and thawing action, which allows the formation of fine air bubbles in the cement hydraulic products. It is widely practiced to carry the air bubbles and relieve and absorb the expansion pressure during freezing by the air bubbles [eg,
"Concrete Engineering Handbook" (published by Asakura Shoten Co., Ltd., 1981 edition), pp. 139-143].
発明が解決しようとする問題点： しかしながら、この空気連行剤はセメント水硬物中で多
くの気泡を発するためにコンクリート等の乾燥収縮が大
きくなること、透水性が大きくなること、さらには中性
化速度が大きくなること等の問題点があり、このため例
えば鉄筋コンクリート構造物の耐久性を損う結果とな
る。Problems to be Solved by the Invention: However, since this air entraining agent generates a large number of bubbles in cement hydraulic material, drying shrinkage of concrete and the like becomes large, water permeability becomes large, and further neutrality However, there is a problem such as an increase in the rate of conversion, which results in, for example, impairing the durability of the reinforced concrete structure.
問題点を解決するための手段： この発明者等はこのような点にかんがみ鋭意研究の結
果、前記一般式（Ｉ）で示される化合物のセメント水硬
物に添加使用すると、セメント水硬物の凍結融解に対す
る耐久性が改善され、しかもセメント水硬物の乾燥収縮
をも低減させるという新知見を得、この発明を完成し
た。Means for Solving the Problems: As a result of earnest studies in view of such points, the present inventors have found that when the compound represented by the general formula (I) is added to the cement hydraulic material, the cement hydraulic material is used. The present invention has been completed by obtaining new knowledge that the durability against freeze-thaw is improved and the drying shrinkage of cement hydraulic material is also reduced.
この発明は、前記一般式（Ｉ）で示される化合物の１種
または２種以上を含むセメント水硬物の凍結融解に対す
る耐久性改善剤であるが、一般式（Ｉ）中、Ｒにおける
アルキル基の例としては例えばメチル、エチル、ｎ−プ
ロピル、イソプロピル、ｎ−ブチル、イソブチル、第３
級ブチル、ｎ−ペンチル、イソペンチル、ヘキシル、ヘ
プチル、オクチル、ノニル、デシル、ドデシル等が挙げ
られ、このうち炭素数１〜12のアルキル基が好ましく、
さらには炭素数１〜６のアルキル基がとくに好ましい。The present invention is a durability improver for freeze-thaw of a cement hydraulic material containing one or more compounds represented by the general formula (I), wherein an alkyl group represented by R in the general formula (I) is used. Examples of include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary
Butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the like, among which an alkyl group having 1 to 12 carbon atoms is preferable,
Further, an alkyl group having 1 to 6 carbon atoms is particularly preferable.
また、一般式（Ｉ）において、式-CH2CH2O-で示される
基を意味するＸと式-CH2CH(CH3)O-で示される基または
式-CH(CH3)CH2O-で示される基を意味するＹとは任意の
順序で結合しているものとする。すなわち、-(X)m(Y)n-
は酸化エチレンまたは酸化プロピレンの単独の付加物お
よび重合物、あるいはブロック重合物またはランダム重
合物の残基を示す。Further, in the general formula (I), X meaning a group represented by the formula —CH 2 CH 2 O— and a group represented by the formula —CH 2 CH (CH 3 ) O— or the formula —CH (CH 3 ) CH. Y, which means a group represented by 2 O-, is bonded in any order. That is,-(X) m (Y) n-
Indicates the residue of a single adduct of ethylene oxide or propylene oxide and a polymer, or a block polymer or a random polymer.
また、前記のように前記一般式（Ｉ）におけるｍは０ま
たは１〜４の整数、ｎは１以上の整数であって、かつｍ
＋ｎが１〜30の整数を意味するが、ｍ＋ｎが30を越える
場合の化合物はセメント水硬物の強度を低下させること
となり、好ましくない。Further, as described above, m in the general formula (I) is 0 or an integer of 1 to 4, n is an integer of 1 or more, and m
+ N means an integer of 1 to 30, but a compound when m + n exceeds 30 is not preferable because it lowers the strength of the cement hydraulic material.
前記一般式（Ｉ）で示される化合物は、フェノールまた
はアルキルフェノールに酸化エチレンおよび（または）
酸化プロピレンのモノマーまたは重合物を反応させて得
られる公知化合物である。The compound represented by the general formula (I) is a phenol or an alkylphenol with ethylene oxide and / or
It is a known compound obtained by reacting a monomer or polymer of propylene oxide.
次に、前記一般式（Ｉ）で示される化合物のうち、代表
的な化合物とその製造例を示す。Next, among the compounds represented by the general formula (I), typical compounds and production examples thereof will be shown.
製造剤１ １容オートクレーブにフェノール282gと触媒として水
酸化ナトリウム１．４ｇを入れ、窒素ガスを導入しなが
ら、徐々に昇温し、100〜110℃で約30分間脱水を行う。
密閉した後酸化プロピレン522gを、温度100〜160℃で圧
入し、付加反応を約３時間かけて行い、更に同温度で30
分間熟成させる。次いで冷却し、開蓋して中和し、精製
すると、淡黄色液体の化合物１および化合物２の混合物
（95：５）765gを得る。 Manufacturing Agent 1 282 g of phenol and 1.4 g of sodium hydroxide as a catalyst are put in a 1-volume autoclave, and the temperature is gradually raised while introducing nitrogen gas, and dehydration is performed at 100 to 110 ° C. for about 30 minutes.
After sealing, 522 g of propylene oxide was press-fitted at a temperature of 100 to 160 ° C., the addition reaction was carried out for about 3 hours, and further 30 minutes at the same temperature.
Let it mature for a minute. It is then cooled, opened, neutralized and purified to give 765 g of a pale yellow liquid mixture of compound 1 and compound 2 (95: 5).
製造例２ 製造例１と同様な方法により、フェノール188g、水酸化
ナトリウム0.9g、酸化プロピレン696gを用いて化合物３
および化合物４の混合物（96：４）829gを得る。Production Example 2 In the same manner as in Production Example 1, 188 g of phenol, 0.9 g of sodium hydroxide and 696 g of propylene oxide were used to give compound 3
And 829 g of a mixture of compounds 4 (96: 4) are obtained.
製造例３ 製造例１と同様な方法により、フェノール141g、水酸化
ナトリウム0.7g、酸化プロピレン783gを用いて化合物５
および化合物６の混合物（96：４）854gを得る。Production Example 3 In the same manner as in Production Example 1, 141 g of phenol, 0.7 g of sodium hydroxide and 783 g of propylene oxide were used to give compound 5
And 854 g of a mixture of compounds 6 (96: 4) are obtained.
製造例４ 製造例１と同様な方法により、メタクレゾールおよびパ
ラクレゾールの混合物（60：40）216g、水酸化ナトリウ
ム1.1g、酸化プロピレン696gを用い化合物７および化合
物８の混合物（96：４）832gを得る。Production Example 4 By the same method as in Production Example 1, 216 g of a mixture of meta-cresol and para-cresol (60:40), 1.1 g of sodium hydroxide and 696 g of propylene oxide were used, and a mixture of Compound 7 and Compound 8 (96: 4) 832 g. To get
製造例５ 製造例１と同様な方法により、２，４−ジメチルフェノ
ール80ｇ、２，５−ジメチルフェノール80g、３，５−
ジメチルフェノール80g、水酸化ナトリウム1.2g、酸化
プロピレン685gを用い化合物９および化合物10の混合物
（96：４）855gを得る。Production Example 5 By the same method as in Production Example 1, 2,4-dimethylphenol 80 g, 2,5-dimethylphenol 80 g, 3,5-
Using dimethylphenol 80 g, sodium hydroxide 1.2 g and propylene oxide 685 g, a mixture (96: 4) of compound 9 and compound 10 (855 g) is obtained.
製造例６ １容オートクレーブに２，４−ジ−ｔ−ブチルフェノ
ール100g、２，６−ジ−ｔ−ジブチルフェノール100gお
よび水酸化ナトリウム1.0gを入れ、窒素ガスを導入しな
がら、徐々に昇温し、100〜110℃で約30分間脱水を行
う。密閉した後、酸化エチレン130gを、温度100〜160℃
にて圧入し、付加反応を約１時間かけて行う。更に同温
度にて酸化プロピレン340gを約３時間かけて付加反応さ
せた後、約30分間熟成させる。冷却後、開蓋して中和
し、精製すると、黄色の液体の化合物11および化合物12
の混合物（97：３）616gを得る。Production Example 6 100 g of 2,4-di-t-butylphenol, 100 g of 2,6-di-t-dibutylphenol and 1.0 g of sodium hydroxide were placed in a 1-volume autoclave, and the temperature was gradually raised while introducing nitrogen gas. Dehydrate at 100-110 ℃ for about 30 minutes. After sealing, 130 g of ethylene oxide, temperature 100-160 ℃
Then, the reaction is carried out for about 1 hour. Further, 340 g of propylene oxide is added at the same temperature for about 3 hours and then aged for about 30 minutes. After cooling, the lid is neutralized and neutralized.
616 g of a mixture of (97: 3) are obtained.
この発明のセメント水硬物の凍結融解に対する耐久性改
善剤のセメント水硬物（セメントペースト、グラウト、
モルタル、コンクリート等の水硬性物質であるセメント
を硬化成分とする混練物）への添加方法は常法による。
すなわち、混練水に添加してもよく、一度練り上がった
セメント水硬物に添加しても良い。また、トラックミキ
サー車によってセメント水硬物が現場に到着した後に添
加しても良い。いずれの添加方法を採用するかは、前記
一般式（Ｉ）で示される化合物の種類および構造物の条
件等に応じて決めれば良い。Cement hydraulic material (cement paste, grout,
The addition method to a kneaded material containing cement, which is a hydraulic substance such as mortar and concrete, as a hardening component) is a conventional method.
That is, it may be added to the kneading water, or may be added to the cement hydraulic material once kneaded. Alternatively, the cement hydraulic material may be added after it arrives at the site by a truck mixer truck. Which addition method is adopted may be determined according to the kind of the compound represented by the general formula (I), the conditions of the structure, and the like.
また、前記一般式（Ｉ）で示される化合物のセメント水
硬物への添加量は０．１〜８％、好ましくは１〜６％
（セメントに対する重量％）程度が適当である。The amount of the compound represented by the general formula (I) added to the cement hydraulic material is 0.1 to 8%, preferably 1 to 6%.
(Wt% with respect to cement) is appropriate.
この発明のセメント水硬物の凍結融解に対する耐久性改
善剤は、セメントの種類、骨材の種類、併用する混和剤
および混和材料の制限を受けない。すなわち、セメント
の種類としては、普通ポルトランドセメント、早強セメ
ント、中庸熱セメント、高炉セメント、フライアッシュ
セメントなど通常市販されているセメントが挙げられ、
また、その一部をフライアッシュ、水砕スラグ粉末、シ
リカ質混合材などと置換することができ、この置換によ
ってこの発明の目的が有利に達成される場合もある。The freeze-thaw durability improver of the cement hydraulic material of the present invention is not limited by the type of cement, the type of aggregate, the admixture used in combination, and the admixture. That is, as the type of cement, ordinary portland cement, early strength cement, moderate heat cement, blast furnace cement, usually commercially available cement such as fly ash cement,
Further, a part thereof can be replaced with fly ash, granulated slag powder, siliceous mixture, etc., and the object of the present invention may be advantageously achieved by this replacement.
さらに、セメント水硬物用減水剤、膨張剤その他公知の
コンクリート又はモルタル用混和材料と併用することも
できる。Further, it can be used in combination with a water reducing agent for cement hydraulic material, a swelling agent and other known admixture materials for concrete or mortar.
発明の効果： この発明の前記一般式（Ｉ）で示される化合物の１種ま
たは２種以上を含むセメント水硬物の凍結融解に対する
耐久性改善剤をセメント水硬物に添加すると、セメント
水硬物の圧縮強度に悪影響を及ぼさずにセメント水硬物
の凍結融解作用に対する耐久性が改善され、しかも従来
のこの目的のために使用されている空気連行剤にみられ
る乾燥収縮が大きくなると、透水性が大きくなること、
さらには中性化速度が大きくなること等の欠点が改善さ
れる。Effect of the Invention: When a durability improver for freeze-thaw of a cement hydraulic fluid containing one or more compounds of the general formula (I) of the present invention is added to the cement hydraulic fluid, the cement hydraulic fluid is added. Improving the durability of the cement hydraulic material against freeze-thaw action without adversely affecting the compressive strength of the product, and increasing the drying shrinkage observed in the air entraining agents conventionally used for this purpose increases the water permeability. The greater the
Furthermore, the drawbacks such as the increased neutralization speed are alleviated.
次にこの発明の効果を試験例により説明する。Next, the effect of the present invention will be described with reference to test examples.
試験例 コンクリートの凍結融解耐久性試験および圧縮 強度試験： (1) コンクリート試験の条件： コンクリート試験は日本工業規格A6204コンクリート用
化学混和剤の規格に準拠して行った。使用したセメント
は普通ポルトランドセメント（小野田セメント、アサノ
セメントおよび住友セメントの３種等量混合、比重：3.
16）、細骨材は富士川産川砂（FM＝2.66、比重：2.6
4）、粗骨材は笠間産砕石（Gamax＝20mm、FM＝6.69、比
重：2.66）である。Test Example Concrete freeze-thaw durability test and compression strength test: (1) Concrete test conditions: The concrete test was conducted in accordance with the Japanese Industrial Standard A6204 Chemical Admixture Standard for Concrete. The cement used was ordinary Portland cement (3 types of equal mixture of Onoda cement, Asano cement and Sumitomo cement, specific gravity: 3.
16), fine aggregate is Fujisawa river sand (FM = 2.66, specific gravity: 2.6)
4), coarse aggregate is crushed stone from Kasama (Gamax = 20mm, FM = 6.69, specific gravity: 2.66).
混練および養生温度は20℃とし、セメント量320kg／
ｍ3、細骨材率50％、スランプ18cmを目標とし、プレー
ンコンクリートの配合を定め、試験例は全てプレーンコ
ンクリートと同一配合とした。Kneading and curing temperature is 20 ℃, cement amount 320kg /
m 3, fine aggregate ratio of 50%, the slump 18cm with the goal defines a formulation of plain concrete, test examples were all plain concrete the same formulation.
下記表中の試験化合物はその所定濃度（セメントに対す
る重量％）を混練水の一部として添加した。The test compounds in the table below were added at a predetermined concentration (% by weight based on cement) as a part of kneading water.
凍結融解試験体は、10×10×40cmとし、日本工業規格A1
132に従って作製した。該試験体には水中養生前の硬化
の初期および水中養生後の比較的硬化の進んだ時期に室
内放置をし、実構造物と同様に乾燥するようにした。す
なわち、打設後20時間で脱型後、20℃、R.H.60±５％の
室内で０、６および24時間それぞれ放置した後、材令２
週まで水中養生を行い、続けて凍結融解試験に供した場
合（表１）と、脱型後材令２週まで水中養生を行った
後、０、２および４日間、それぞれ上記条件の室内に放
置し、続いて凍結融解試験を行った場合（表２）の２つ
の場合について、凍結融解耐久性を調べた。凍結融解試
験は日本工業規格A6204付属書２に従い、＋５℃〜−18
℃の凍結融解のくり返しとし、１サイクル約３．５時間
で行い、25サイクル毎に相対動弾性係数を測定した。な
お、相対動弾性係数は日本工業規格A1127に従って、た
わみ振動の一次共鳴振動数を求め次式によって算出し
た。Freeze-thaw test specimen is 10 × 10 × 40 cm, Japanese Industrial Standard A1
Produced according to 132. The test body was allowed to stand indoors at the early stage of curing before underwater curing and at the stage of relatively advanced curing after underwater curing, and dried in the same manner as the actual structure. That is, after 20 hours from casting, the mold is removed, and after it is left in a room at 20 ° C and RH60 ± 5% for 0, 6 and 24 hours respectively,
When underwater curing was performed for up to a week, and subsequently subjected to a freeze-thaw test (Table 1), and after underwater curing for up to 2 weeks after demolding, the chamber was subjected to the above conditions for 0, 2 and 4 days, respectively. The freeze-thaw durability was investigated in two cases, that is, when the sample was left standing and then subjected to a freeze-thaw test (Table 2). Freeze-thaw test is in accordance with Japanese Industrial Standard A6204 Appendix 2, + 5 ℃ to -18
Repeated freeze-thawing at 0 ° C was performed for about 3.5 hours per cycle, and the relative dynamic elastic modulus was measured every 25 cycles. The relative dynamic elastic modulus was calculated according to the following formula by obtaining the primary resonance frequency of flexural vibration according to Japanese Industrial Standard A1127.
ｆｎ：各サイクルでの試験体の一次共鳴振動数 ｆｏ：凍結融解試験開始前の一次共鳴振動数 圧縮強度試験体はφ10×20cmとし、日本工業規格A1132
に従って作製し、材令１日目にキャッピングを行い、材
令２日で脱型後、20℃の水中養生を行った。圧縮強度は
材令７日および28日で日本工業規格A1108に従ってそれ
ぞれ測定した。 f n : Primary resonance frequency of test body in each cycle f o : Primary resonance frequency before start of freeze-thaw test Compressive strength test body is φ10 × 20 cm, Japanese Industrial Standard A1132
According to the above procedure, capping was carried out on the first day of the material age, the mold was removed on the second day of the material age, and then aged in water at 20 ° C. The compressive strength was measured on the 7th and 28th days according to Japanese Industrial Standard A1108.
(2) 試験結果： 結果は次表（表１および表２）に示す通りである。(2) Test results: The results are as shown in the following tables (Table 1 and Table 2).
上記表からも明らかなように、前記一般式（Ｉ）で示さ
れる化合物は圧縮強度に悪影響を及ぼさずに、添加量に
応じてセメント水硬物の凍結融解作用に対する耐久性を
改善できることが判る。そしてセメント水硬物の硬化の
初期あるいは比較的硬化の進んだ時期のいずれにおいて
も凍結融解作用を受ける前に僅かな放置時間を設けるこ
とによって、その効果を一層発揮させることができる。 As is clear from the above table, it is understood that the compound represented by the general formula (I) can improve the durability of the cement hydraulic material against the freeze-thaw action depending on the amount added, without adversely affecting the compressive strength. . The effect can be further exerted by providing a short standing time before receiving the freeze-thaw action at either the early stage of hardening of the cement hydraulic material or the time of relatively advanced hardening.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐久田 昌治 東京都江東区南砂２丁目５番14号 株式会 社竹中工務店技術研究所内 (72)発明者 浦野 敏晴 東京都江東区南砂２丁目５番14号 株式会 社竹中工務店技術研究所内 (72)発明者 遠藤 脩造 東京都荒川区南千住６−57−15 (72)発明者 藤岡 恵輔 神奈川県川崎市宮前区宮前平３―９―７ (56)参考文献 特開 昭59−232952（ＪＰ，Ａ) 特開 昭62−91449（ＪＰ，Ａ) 特開 昭62−91452（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Sakuta 2-5-14 Minamisuna, Koto-ku, Tokyo Inside the Takenaka Corporation Technical Research Institute (72) Inventor Toshiharu Urano 2-5 Minamisuna, Koto-ku, Tokyo No. 14 Incorporated Takenaka Corp. Technical Research Institute (72) Inventor Sozo Endo 6-57-15 Minamisenju, Arakawa-ku, Tokyo (72) Inventor Keisuke Fujioka 3-9-7, Miyamaedaira, Miyamae-ku, Kawasaki-shi, Kanagawa ( 56) References JP-A-59-232952 (JP, A) JP-A-62-91449 (JP, A) JP-A-62-91452 (JP, A)
Claims (1)
を、Ｘは式-CH2CH2O-で示される基を、Ｙは式-CH2CH(CH
3)O-で示される基または式-CH(CH3)CH2O-で示される基
を、ｍは０または１〜４の整数、ｎは１以上の整数であ
って、かつｍ＋ｎが１〜30の整数をそれぞれ意味し、Ｘ
およびＹは任意の順序で結合しているものとする］で示
される化合物の１種または２種以上を含むことを特徴と
するセメント水硬物の凍結融解に対する耐久性改善剤。1. A general formula [Wherein R 1 and R 2 are each a hydrogen atom or an alkyl group, X is a group represented by the formula —CH 2 CH 2 O—, and Y is a group represented by the formula —CH 2 CH (CH
Group or the formula -CH (CH 3) CH 2 O- a group represented indicated by 3) O-, m is 0 or an integer from 1 to 4, n represents an integer of 1 or more, is and m + n 1 Each means an integer of ~ 30, X
And Y are bonded in any order.] A freeze-thaw durability improver for cement hydraulic fluid, comprising one or more compounds represented by the formula [1].
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8933886A JPH0637317B2 (en) | 1986-04-17 | 1986-04-17 | Durability improver for freeze-thaw cement cement |
| EP87104781A EP0242646A1 (en) | 1986-04-17 | 1987-04-01 | A durability improving agent for cement compositions and a method for improving durability of cement compositions |
| KR870003654A KR870009962A (en) | 1986-04-17 | 1987-04-16 | Durability improving agent for cement composition and method for improving durability of cement composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8933886A JPH0637317B2 (en) | 1986-04-17 | 1986-04-17 | Durability improver for freeze-thaw cement cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62246852A JPS62246852A (en) | 1987-10-28 |
| JPH0637317B2 true JPH0637317B2 (en) | 1994-05-18 |
Family
ID=13967905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8933886A Expired - Lifetime JPH0637317B2 (en) | 1986-04-17 | 1986-04-17 | Durability improver for freeze-thaw cement cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637317B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0678185B2 (en) * | 1986-05-29 | 1994-10-05 | 株式会社竹中工務店 | Durability improver for cement hydraulic products |
-
1986
- 1986-04-17 JP JP8933886A patent/JPH0637317B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62246852A (en) | 1987-10-28 |
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