Dispersant composition for hydraulic compositions for centrifugal molding

Abstract

A method for producing a hardened product of a hydraulic composition, includes mixing water, a hydraulic powder, a dispersant composition, and an aggregate to prepare a hydraulic composition, filling the hydraulic composition into a mold, and steam curing, in the mold, the hydraulic composition filled into the mold. The dispersant composition includes (A) a formaldehyde naphthaienesulfonate condensate or a salt thereof, (B) a compound having an alkylenoxy group, and optionally (C) a polycarboxylic acid-based copolymer, in particular proportions.

Claims

1. A method for producing a hardened product of a hydraulic composition, the method comprising: mixing water, a hydraulic powder, a dispersant composition, and an aggregate to prepare a hydraulic composition; filling the hydraulic composition into a mold; and steam curing, in the mold, the hydraulic composition filled into the mold; wherein: the dispersant composition comprises (A), (B) and optionally (C): (A) a formaldehyde naphthalenesulfonate condensate or a salt thereof; (B) one or more compounds selected from compounds represented by formula (B1), compounds represented by formula (B2), compounds represented by formula (B3), and compounds represented by formula (B4); ##STR00008## wherein: R.sup.11, R.sup.21, R.sup.31 and R.sup.41 each independently represent a hydrocarbon group having a carbon number of 4 or more and 27 or less; R.sup.22 represents a hydrogen atom or an alkyl group having a carbon number of 1 or more and 3 or less; R.sup.32 and R.sup.33 are the same or different, and each represents a hydrogen atom or an alkyl group having a carbon number of 1 or more and 3 or less; X represents O or COO; AO represents an alkyleneoxy group having a carbon number of 2 or more and 4 or less; n.sub.1 represents an average number of moles of added AO and is 1 or more and 200 or less; n.sub.2 represents an average number of moles of added AO and is 1 or more and 200 or less; n.sub.3 and n.sub.4 are the same or different, and each represents an average number of moles of added AO and is 0 or more, and the total of n.sub.3 and n.sub.4 is 1 or more and 200 or less; Y.sup.1 and Y.sup.2 are the same or different, and each represents a hydrogen atom or SO.sub.3M, and at least one of Y.sup.1 and Y.sup.2 is SO.sub.3M; n.sub.5 and n.sub.6 are the same or different, and each represents an average number of moles of added AO and is 0 or more, and the total of n.sub.5 and n.sub.6 is 1 or more and 200 or less; when n.sub.5 is 0, Y.sup.1 is a hydrogen atom; and when n.sub.6 is 0, Y.sup.2 is a hydrogen atom; and M is a counter ion; and (C) a polycarboxylic acid-based copolymer; the hydraulic composition has a water/hydraulic powder ratio of 10 mass % or more and 53 mass % or less; a total amount of (A) and (B) in the hydraulic composition is 025 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the hydraulic powder; the dispersant composition comprises (A) and (B) so that an amount of (B) is 1 mass % or more and 60 mass % or less relative to a total amount of (A) and (B); and the dispersant composition comprises (C) in an amount of 30 mass % or less based on solid content.

2. The method according to claim 1, wherein the dispersant composition comprises (A) and (C) so that a mass ratio of (C) to (A), (C)/(A) is over 0/100 and 50/50 or less.

3. The method according to claim 1, wherein the dispersant composition comprises (C) in an amount of 1 mass % or more and 30 mass % or less based on solid content.

4. The method according to claim 1, wherein (B) comprises one or more compounds selected from compounds represented by formula (B1), compounds represented by formula (B2), and compounds represented by formula (B3).

5. The method according to claim 1, wherein the dispersant composition comprises (A) in an amount of 1 mass % or more and 99 mass % or less based on solid content.

6. The method according to claim 1, wherein the dispersant composition comprises (B) in an amount of 2 mass % or more and 90 mass % or less based on solid content.

7. The method according to claim 1, wherein: the dispersant composition is in the form of a liquid comprising water; and the dispersant composition comprises (A) in an amount of 1 mass % or more and 50 mass % or less.

8. The method according to claim 1, wherein: the dispersant composition is in the form of a liquid comprising water; and the dispersant composition comprises (B) in an amount of 1 mass % or more and 60 mass % or less.

9. The method according to claim 1, wherein (A) is present in the hydraulic composition in an amount of 0.15 parts by mass or more and 9.9 parts by mass or less relative to 100 parts by mass of the hydraulic powder.

10. The method according to claim 1, wherein (B) is present in the hydraulic composition in an amount of 0.0025 parts by mass or more and 6 parts by mass or less relative to 100 parts by mass of the hydraulic powder.

11. The method according to claim 3, wherein the dispersant composition comprises (A) and (C) so that a mass ratio of (C) to (A), (C)/(A), is over 0/100 and 50/50 or less.

12. The method according to claim 3, wherein (B) comprises one or more compounds selected from compounds represented by formula (B1), compounds represented by formula (B2), and compounds represented by formula (B3).

13. The method according to claim 3, wherein the dispersant composition comprises (A) in an amount of 1 mass % or more and 99 mass % or less based on solid content.

14. The method according to claim 3, wherein the dispersant composition comprises (B) in an amount of 2 mass % or more and 90 mass % or less based on solid content.

15. The method according to claim 3, wherein: the dispersant composition is in the form of a liquid comprising water; and the dispersant composition comprises (A) in an amount of 1 mass % or more and 50 mass % or less.

16. The method according to claim 3, wherein: the dispersant composition is in the form of a liquid comprising water; and the dispersant composition comprises 03) in an amount of 1 mass % or more and 60 mass % or less.

17. The method according to claim 3, wherein (A) is present in the hydraulic composition in an amount of 0.15 parts by mass or more and 9.9 parts by mass or less relative to 100 parts by mass of the hydraulic powder.

18. The method according to claim 3, wherein (B) is present in the hydraulic composition in an amount of 0.0025 parts by mass or more and 6 parts by mass or less relative to 100 parts by mass of the hydraulic powder.

Description

EXAMPLES

Example 1 and Comparative Example 1

(1) (1) Concrete Formulation

(2) Concrete formulation is shown in Table 1. In Table 1, W/(C+P) is a ratio of water/hydraulic powder.

(3) TABLE-US-00001 TABLE 1 W/(C + P) Unit amount (kg/m.sup.3) (mass %) W C P S G 18.7 125 600 65 595 1100

(4) Components in the table are as follows.

(5) W: water from public water supply system in Wakayama

(6) C: early strength portland cement (mixture of two types: early strength portland cement manufactured by Taiheiyo Cement Corporation/early strength portland cement manufactured by Sumitomo Osaka Cement Co., Ltd=1/1, mass ratio), density: 3.14 g/cm.sup.3

(7) P: high-strength admixture (gypsum based)

(8) S: fine aggregate, crushed sand

(9) G: coarse aggregate, crushed stone

(10) W in Table 1 contains a component selected from components (A) to (C) used in Table 2, and the amounts of these components are very small relative to concrete formulation. Thus, they are incorporated into the amount of W, and then, W/(C+P) was calculated.

(11) Components (A) to (C) in Table 2 are as follows.

(12) [Component (A)]

(13) NSF: sodium salt of a formaldehyde naphthalenesulfonate condensate, weight average molecular weight: 15000

(14) This NSF was prepared based on Example of JP-A 48-11737.

(15) [Component (B)]

(16) AES (30): polyoxyethylene (30) oleyl ether ammonium sulfate AES (60): polyoxyethylene (60) oleyl ether ammonium sulfate AE (30): polyoxyethylene (30) oleyl ether AE (60): polyoxyethylene (60) oleyl ether Amite (20): polyoxyethylene (20) stearyl amine ether

(17) Numbers in parentheses for components (B) indicate an average number of moles of added ethylene oxide (the same applies to the following Examples and Comparative Examples).

(18) [Component (C)]

(19) PCE: copolymer of methacrylic acid/methoxy polyethylene glycol monomethacrylate (average number of moles of added ethylene oxide of 120)=95/5 (molar ratio), weight average molecular weight: 20000

(20) This PCE was prepared based on Production Example 12 of JP-A 8-12397.

(21) (2) Method for Preparing Concrete for Centrifugal Molding

(22) Dispersant compositions containing components (A), (B) and (C) and water were prepared to satisfy their added amounts in Table 2. A dispersant composition was added to water (W) as a material for concrete formulation in Table 1, and kneaded with other materials for concrete formulation by a biaxial pug mill for 4 minutes, thereby preparing concrete for centrifugal molding. The added amount is equal to a mixing amount of each component (the same applies to the following Examples and Comparative Examples).

(23) (3) Moldability

(24) 15 kg of concrete for centrifugal molding was placed in a centrifugal molding mold (inner diameter: 20 cmheight: 30 cm), and centrifugally compacted by the first speed of 1 G for 3 minutes, the second speed of 3 G for 3 minutes, the third speed of 9 G for 2 minutes, and the fourth speed of 25 G for 3 minutes. Thereafter, steam curing including presteaming at 20 C. for 3 hours; temperature rise of 20 C. per hour; keeping at 70 C. for 6 hours; and then cooling, was conducted.

(25) After being demolded, the hardened product was measured for the thickness (mm) of concrete at 4 positions of each of the upper and lower parts thereof (8 positions in total), and evaluated according to the following standard.

(26) AA: The difference between the maximum value and the minimum value of the thickness at the 8 positions was less than 3 mm

(27) A: The difference between the maximum value and the minimum value of the thickness at the 8 positions was 3 mm or more and 5 mm or less (in a state where the paste layer on the inner surface was soft and accumulated in a small amount on the lower part)

(28) C: The difference between the maximum value and the minimum value of the thickness at the 8 positions was over 5 mm (in a state where the shape of the product was not able to be retained due to considerable droop or rock pocket)

(29) (4) Compressive Strength

(30) A compressive area was obtained from an average of thicknesses of the hardened product, which was used for evaluation of moldability. The same hardened product was used to measure a compressive stress thereof 7 days after the kneading in accordance with JIS A 1108. A compressive strength was calculated by the equation, compressive strength=compressive stress/compressive area. The evaluation on compressive strength was not conducted on some of Comparative Examples having C for moldability evaluation.

(31) Results thereof are shown in Table 2.

(32) TABLE-US-00002 TABLE 2 Component (A) Component (B) Component (C) Total Molar Added Added Added added (B)/[(A) ratio of amount amount amount amount + (B)/ Compressive (part by (part by (part by (part by (B)] naphthalene strength Type mass) Type mass) Type mass) mass) (mass %) ring (%) (N/mm.sup.2) Moldability Exam- 1-1 NSF 0.85 AES (30) 0.05 0.90 5.6 0.85 131 AA ples 1-2 0.72 0.08 0.80 10.0 1.60 133 AA 1-3 0.66 0.17 0.83 20.5 3.70 133 AA 1-4 0.56 0.14 0.70 20.0 3.59 135 AA 1-5 0.49 0.21 0.70 30.0 6.16 136 AA 1-6 0.45 0.3 0.75 40.0 9.58 134 AA 1-7 0.38 0.37 0.75 49.3 14.00 131 AA 1-8 0.49 AES (60) 0.21 0.70 30.0 3.45 135 AA 1-9 0.80 AE (30) 0.20 1.0 20.0 3.81 131 AA 1-10 0.63 AE (60) 0.27 0.90 30.0 3.57 132 AA 1-11 0.56 Amite (20) 0.19 0.75 25.3 7.15 132 AA 1-12 0.38 AES (30) 0.12 PCE 0.10 0.60 24.0 4.54 135 AA 1-13 0.35 AES (60) 0.18 PCE 0.07 0.60 34.0 4.15 136 AA Com- 1-1 NSF 1.5 1.5 0 65.2 C par- (rock ative pockets) Exam- 1-2 2.5 2.5 0 120 AA ples 1-3 3.0 3.0 0 116 A 1-4 PCE 0.50 0.50 not measured C 1-5 1.0 1.0 not measured C 1-6 NSF 0.45 PCE 0.15 0.60 0 not measured C (not kneable) 1-7 AES (30) 0.15 0.15 100 not measured C 1-8 0.83 0.83 100 not measured C

(33) In Table 2, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of the total of cement (C) and high strength admixture (P).

(34) Further, in Table 2, the total added amount is an added amount of the total of components (A), (B) and (C) in terms of solid content relative to 100 parts by mass of the total of cement (C) and high strength admixture (P).

(35) Further, in Table 2, (B)/[(A)+(B)] is a ratio (mass %) of a content of component (B) relative to the total content of components (A) and (B) in the dispersant composition (the same applies to the following Examples and Comparative Examples).

(36) Further, in Table 2, a molar ratio of (B)/naphthalene ring is a molar ratio (%) of the total amount of component (B) relative to a naphthalene ring-containing monomer unit in component (A) (the same applies to the following Examples and Comparative Examples).

(37) From results of Table 2, it is understood that combined use of components (A) and (B) of the present invention provides a good centrifugal moldability and an improvement in the strength of the hardened product after centrifugal molding.

Example 2 and Comparative Example 2

(38) (1) Mortar Formulation

(39) Mortar formulation is shown in Table 3.

(40) TABLE-US-00003 TABLE 3 W/C Unit amount (g/batch) (mass %) W C S 35 140 400 700

(41) Components in the table are as follows.

(42) W: water from public water supply system in Wakayama

(43) C: PCB-40 manufactured by Nghi Son Cement Corporation (Vietnam)

(44) S: fine aggregate (pit sand from Joyo area, particles having a particle size of 3.5 mm or more were removed)

(45) W in Table 3 contains components selected from components (A) and (B) used in Tables 5 and 6, and amounts of these components were very small relative to mortar formulation. Thus, they are incorporated into the amount of W and W/C was calculated.

(46) Components (A) and (B) in Tables 5 and 6 are as follows.

(47) [Component (A)]

(48) NSF: sodium salt of a formaldehyde naphthalenesulfonate condensate, weight average molecular weight: 15000

(49) This NSF was prepared based on Example of JP-A 48-11737.

(50) [Component (B)]

(51) Components (B) shown in Table 4 were used. B-1 is a comparative compound of component (B), but included in Table 4 for convenience.

(52) (2) Method for Preparing Mortar

(53) Dispersant compositions containing components (A) and (B) and water were prepared to satisfy their added amounts in Tables 5 and 6. Temperatures of raw materials for mortar formulation and the temperature of working environment (room temperature) were both set to 30 C.

(54) Into a mortar mixer (universal mixing stirrer, model: 5DM-03- manufactured by Dalton Corporation), a cement (C) and a fine aggregate (S) were fed and dry-mixed for 10 seconds at a low speed rotation (63 rpm) of the mortar mixer, and the mixing water (W) was added. The mixing water (W) contained a dispersant composition and an antifoaming agent. Then, the mixture was subjected to main kneading for 120 seconds at a low speed rotation (63 rpm) of the mortar mixer, so that a mortar was prepared.

(55) As the antifoaming agent, Foamlex 797 (manufactured by Nicca Chemical Co., Ltd.) was added in an amount of 3 mass % relative to component (B).

(56) (3) Fluidity

(57) In accordance with the test method of JIS R 5201, the flow of the prepared mortar was measured. Added amounts of components (A) and (B) were adjusted so that the mortar flow was 180 to 200 mm.

(58) (4) Strength

(59) Mortar obtained by kneading was filled into a mold with an inner diameter of 50 mma height of 100 mm, hardened by a production method including steam curing, and the strength of the hardened product of the obtained mortar was tested in accordance with JIS A 1108 Method of test for compressive strength of concrete.

(60) In obtaining a hardened product, steam curing was conducted after presteaming was conducted for a predetermined period shown in Tables 5 and 6. A presteaming period is a period from addition of mixing water (W) to a mortar mixer at the setting temperature (30 C. for this case) to the start of temperature rise for steam curing. The presteaming was carried out by filling a hydraulic composition into a mold and allowing the mortar-filled mold to stand at the setting temperature (30 C. for this case). The same applies to the following Examples and Comparative Examples.

(61) Steam curing was carried out at a humidity setting of 100% by use of a thermo-hygrostat PR-3J manufactured by Espec Corporation.

(62) Temperature rise for steam curing was conducted for 0.5 hours from 30 C. to 70 C., which were setting temperatures for the thermo-hygrostat. Next, steam curing was conducted for 3.5 hours at a constant temperature of 70 C., which was a setting temperature for the thermo-hygrostat. Temperature drop for steam curing was conducted for 0.5 hours from 70 C. to 30 C., which were setting temperatures for the thermo-hygrostat. After the setting temperature of the thermo-hygrostat reached 30 C., the hardened product was demolded and, immediately, the strength thereof was measured.

(63) TABLE-US-00004 TABLE 4 Component (B) Mark Type Carbon No.* B-1 Polyoxyethylene (7) oleyl ether 18 B-2 Polyoxyethylene (9) oleyl ether 18 B-3 Polyoxyethylene (13.5) oleyl ether 18 B-4 Polyoxyethylene (30) oleyl ether 18 B-5 Polyoxyethylene (60) oleyl ether 18 B-6 Polyoxyethylene (7) oleyl ether ammonium sulfate 18 B-7 Polyoxyethylene (9) oleyl ether ammonium sulfate 18 B-8 Polyoxyethylene (13.5) oleyl ether ammonium 18 sulfate B-9 Polyoxyethylene (30) oleyl ether ammonium sulfate 18 B-10 Polyoxyethylene (60) oleyl ether ammonium sulfate 18 B-11 Polyoxyethylene (11) stearyl ether ammonium 18 sulfate B-12 Polyoxyethylene (50) stearyl ether ammonium 18 sulfate B-13 Polyoxyethylene (20) stearyl amine ether 18 ammonium sulfate B-14 Polyoxyethylene (100) stearyl amine ether 18 ammonium sulfate B-15 Polyoxyethylene (4) lauryl ether ammonium sulfate 12 B-16 Polyoxyethylene (23) lauryl ether ammonium sulfate 12 B-17 Polyoxyethylene (5) decyl ether ammonium sulfate 10 B-18 Polyoxyethylene (11) 2-ethyl hexyl ether 8 ammonium sulfate B-19 Polyoxyethylene (13) distyrenated phenyl ether 22 ammonium sulfate B-20 Polyoxyethylene (19) distyrenated phenyl ether 22 ammonium sulfate B-21 Polyoxyethylene (30) distyrenated phenyl ether 22 ammonium sulfate B-22 Polyoxyethylene (64) distyrenated phenyl ether 22 ammonium sulfate B-23 Polyoxyethylene (14) tribenzyl phenyl ether 27 ammonium sulfate B-24 Polyoxyethylene (13) distyrenated phenyl ether 22 B-25 Polyoxyethylene (19) distyrenated phenyl ether 22 B-26 Butyl diglycol 4 B-1 Methyl diglycol 1 *Carbon number: carbon number of R.sup.11, R.sup.21, R.sup.31 or R.sup.41 in general formulas (B1) to (B4)

(64) TABLE-US-00005 TABLE 5 Component (A) Component (B) Molar Total Added Added (B)/[(A) ratio of added Pre- Com- Com- amount amount + (B)/ amount Mortar Curing steaming pressive pressive (part by (part by (B)] naphthalene (part by flow con- time strength strength Type mass) Type mass) (mass %) ring (%) mass) (mm) dition (hr.) (MPa) ratio(%) Exam- 2-1 NSF 0.496 B-1 0.124 20 10.5 0.62 188 steam 2.0 16.8 130 ples 2-2 NSF 0.496 B-2 0.124 20 9.1 0.62 190 steam 2.0 19.8 153 2-3 NSF 0.496 B-3 0.124 20 7.0 0.62 192 steam 2.0 20.5 159 2-4 NSF 0.480 B-4 0.120 20 3.8 0.60 192 steam 2.0 16.8 130 2-5 NSF 0.480 B-5 0.120 20 2.1 0.60 194 steam 2.0 15.4 119 2-6 NSF 0.496 B-6 0.124 20 8.8 0.62 192 steam 2.0 24.4 189 2-7 NSF 0.496 B-7 0.124 20 7.8 0.62 194 steam 2.0 28.5 221 2-8 NSF 0.496 B-8 0.124 20 6.2 0.62 195 steam 2.0 27.0 209 2-9 NSF 0.480 B-9 0.120 20 3.6 0.60 192 steam 2.0 24.2 188 2-10 NSF 0.480 B-10 0.120 20 2.0 0.60 194 steam 2.0 22.8 177 2-11 NSF 0.496 B-11 0.124 20 7.0 0.62 190 steam 2.0 27.5 213 2-12 NSF 0.480 B-12 0.120 20 2.3 0.60 194 steam 2.0 23.4 181 2-13 NSF 0.496 B-13 0.124 20 4.8 0.62 192 steam 2.0 27.7 215 2-14 NSF 0.480 B-14 0.120 20 1.3 0.60 191 steam 2.0 24.4 189 2-15 NSF 0.512 B-15 0.128 20 12.7 0.64 188 steam 2.0 21.4 166 2-16 NSF 0.512 B-16 0.128 20 4.6 0.64 189 steam 2.0 25.1 195 2-17 NSF 0.528 B-17 0.132 20 12.3 0.66 185 steam 2.0 19.4 150 2-18 NSF 0.576 B-18 0.144 20 8.3 0.72 188 steam 2.0 15.2 118 2-19 NSF 0.496 B-19 0.124 20 6.1 0.62 191 steam 2.0 28.2 219 2-20 NSF 0.496 B-20 0.124 20 4.8 0.62 192 steam 2.0 28.8 223 2-21 NSF 0.496 B-21 0.124 20 3.5 0.62 192 steam 2.0 30.0 233 2-22 NSF 0.496 B-22 0.124 20 1.9 0.62 194 steam 2.0 26.7 207 2-23 NSF 0.496 B-23 0.124 20 5.5 0.62 190 steam 2.0 28.7 222 2-24 NSF 0.496 B-24 0.124 20 6.9 0.62 188 steam 2.0 21.7 168 2-25 NSF 0.496 B-25 0.124 20 5.3 0.62 186 steam 2.0 21.4 166 2-26 NSF 0.656 B-26 0.164 20 24.2 0.82 188 steam 2.0 13.7 106 Com- 2-1 NSF 0.660 0 0.0 0.66 190 steam 2.0 12.9 100 parative 2-2 NSF 0.656 B-1 0.164 20 29.1 0.82 189 steam 2.0 12.8 99 Exam- ples

(65) TABLE-US-00006 TABLE 6 Component (A) Component (B) Molar Total Added Added (B)/[(A) ratio of added Pre- Com- Com- amount amount + (B)/ amount Mortar Curing steaming pressive pressive (part by (part by (B)] naphthalene (part by flow con- time strength strength Type mass) Type mass) (mass %) ring (%) mass) (mm) dition (hr.) (MPa) ratio(%) Exam- 2-11 NSF 0.496 B-11 0.124 20 7.0 0.62 190 steam 2.0 27.5 213 ples 2-27 NSF 0.558 B-11 0.062 10 3.1 0.62 188 steam 2.0 23.1 179 2-28 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 2.0 21.8 169 2-29 NSF 0.647 B-11 0.013 2 0.6 0.66 185 steam 2.0 16.5 128 2-30 NSF 0.420 B-11 0.180 30 12.0 0.60 192 steam 2.0 25.0 194 2-31 NSF 0.390 B-11 0.260 40 18.6 0.65 190 steam 2.0 19.4 150 2-32 NSF 0.400 B-11 0.400 50 27.9 0.80 192 steam 2.0 16.4 127 2-33 NSF 0.480 B-11 0.720 60 41.8 1.20 184 steam 2.0 15.2 118 2-19 NSF 0.496 B-19 0.124 20 6.1 0.62 191 steam 2.0 28.2 219 2-34 NSF 0.558 B-19 0.062 10 2.7 0.62 188 steam 2.0 28.8 223 2-35 NSF 0.608 B-19 0.032 5 1.3 0.64 192 steam 2.0 26.2 203 2-36 NSF 0.647 B-19 0.013 2 0.4 0.66 192 steam 2.0 19.4 150 Com- 2-1 NSF 0.660 0 0.0 0.66 190 steam 2.0 12.9 100 parative 2-3 NSF 0.480 B-11 1.120 70 65.3 1.60 181 steam 2.0 13.3 103 Exam- ples

(66) In Tables 5 and 6, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(67) Further, in Tables 5 and 6, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).

(68) Further, in Tables 5 and 6, the compressive strength ratio is a relative value when the compressive strength of Comparative Example 2-1 was taken as 100%.

Example 3 and Comparative Example 3

(69) Mortar was prepared in the same manner as in Example 2 by changing the mortar formulation as shown in Table 7, and the fluidity and the strength were evaluated. Results are shown in Table 8.

(70) TABLE-US-00007 TABLE 7 W/C Unit amount (g/batch) (mass %) W C S 35 140 400 700 40 160 400 700 45 180 400 700 50 200 400 700 55 220 400 700

(71) TABLE-US-00008 TABLE 8 Component (A) Component (B) Molar Total Com- Added Added (B)/[(A) ratio of added Pre- Com- pressive W/C amount amount + (B)/ amount Mortar Curing steaming pressive strength (mass (part by (part by (B)] naphthalene (part by flow con- time strength ratio %) Type mass) Type mass) (mass %) ring (%) mass) (mm) dition (hr.) (MPa) (%) Com- 2-1 35 NSF 0.660 0 0.0 0.66 190 steam 2.0 12.9 100 parative Example Example 2-28 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 2.0 21.8 169 Example 2-34 35 NSF 0.558 B-19 0.062 10 2.7 0.62 188 steam 2.0 28.8 223 Com- 3-1 40 NSF 0.560 0 0.0 0.56 192 steam 2.0 12.6 100 parative Example Example 3-1 40 NSF 0.513 B-11 0.027 5 1.5 0.54 188 steam 2.0 17.6 140 Example 3-2 40 NSF 0.486 B-19 0.054 10 2.7 0.54 185 steam 2.0 19.2 152 Com- 3-2 45 NSF 0.440 0 0.0 0.44 191 steam 2.0 12.5 100 parative Example Example 3-3 45 NSF 0.399 B-11 0.021 5 1.5 0.42 193 steam 2.0 14.2 114 Example 3-4 45 NSF 0.378 B-19 0.042 10 2.7 0.42 192 steam 20 15.1 121 Com- 3-3 50 NSF 0.280 0 0.0 0.28 185 steam 2.0 11.8 100 parative Example Example 3-5 50 NSF 0.257 B-11 0.013 5 1.5 0.27 187 steam 2.0 12.6 107 Example 3-6 50 NSF 0.243 B-19 0.027 10 2.7 0.27 189 steam 2.0 12.8 108 Test 3-1 55 NSF 0.220 0 0.0 0.22 185 steam 2.0 10.4 100 Example Test 3-2 55 NSF 0.209 B-11 0.011 5 1.5 0.22 190 steam 2.0 10.4 100 Example Test 3-3 55 NSF 0.198 B-19 0.022 10 2.7 0.22 192 steam 2.0 10.4 100 Example Test 3-4 55 NSF 0.176 B-19 0.044 10 6.1 0.22 198 steam 2.0 10.3 99 Example

(72) In Table 8, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(73) Further, in Table 8, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).

(74) Further, in Table 8, the compressive strength ratio is a relative value regarding each W/C, when the compressive strength of Comparative Example or Test Example 3-1 was taken as 100%.

(75) When W/C was 55 mass %, the total added amount of components (A) and (B) for obtaining a predetermined mortar flow was 0.22 parts by mass. In this case, even combined use of components (A) and (B) did not change the compressive strength in comparison with the case where only component (A) was added. In addition, for mortar formulation with W/C being 55 mass %, when components (A) and (B) were added in total in amount of 0.27 parts by mass, material segregation was generated and fine aggregates (sand) were settled in the lower layer of the hardened product. This prevented accurate measurement.

(76) Meanwhile, when W/C was 35 mass %, 45 mass % or 50 mass %, the total added amount of components (A) and (B) to provide a predetermined mortar flow had to be 0.25 parts by mass or more. In this case, it is understood that combined use of components (A) and (B) increased the compressive strength. In addition, for mortar formulation with W/C being 35 mass %, when components (A) and (B) were added in total in an amount of 0.22 parts by mass, no fluidity was developed and a hardened product for strength measurement could not be produced.

Example 4 and Comparative Example 4

(77) Mortar was prepared in the same manner as in Example 2 by changing the types of cement as shown in Table 9, and the fluidity and the strength were evaluated. In some examples, temperature of raw materials for mortar formulation, temperatures of working environment, and temperatures at the start of temperature rise and at the end of temperature drop for steam curing were changed to 20 C. Results are shown in Table 9.

(78) TABLE-US-00009 TABLE 9 Component Component (A) (B) (B)/ Molar Total Added Added [(A) ratio of added Com- amount amount + (B)/ amount Mor- Pre- Com- pressive Type (part (part (B)] naphtha- (part tar Curing steaming pressive strength of Temp.* by by (mass lene by flow con- time strength ratio cement ( C.) Type mass) Type mass) %) ring (%) mass) (mm) dition (hr.) (MPa) (%) Com- 4-1 Thai 30 NSF 0.440 0 0.0 0.44 192 steam 2.0 22.1 100 parative Example Example 4-1 Thai 30 NSF 0.418 B-11 0.022 5 1.5 0.44 191 steam 2.0 28.3 128 Com- 4-2 Vietnam 20 NSF 0.540 0 0.0 0.54 188 steam 2.0 13.2 100 parative Example Example 4-2 Vietnam 20 NSF 0.513 B-11 0.027 5 1.5 0.54 192 steam 2.0 18.3 139 Com- 4-3 Malaysia 30 NSF 0.570 0 0.0 0.57 186 steam 2.0 16.4 100 parative Example Example 4-3 Malaysia 30 NSF 0.523 B-11 0.027 5 1.5 0.55 188 steam 2.0 22.1 135 Com- 4-4 Indonesia 30 NSF 0.600 0 0.0 0.60 195 steam 2.0 14.3 100 parative Example Example 4-4 Indonesia 30 NSF 0.551 B-11 0.029 5 1.5 0.58 193 steam 2.0 23.7 166 Com- 2-1 Vietnam 30 NSF 0.660 0 0.0 0.66 190 steam 2.0 12.9 100 parative Example Example 2-28 Vietnam 30 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 2.0 21.8 169 Com- 4-5 China 20 NSF 0.800 0 0.0 0.80 188 steam 2.0 10.1 100 parative Example Example 4-5 China 20 NSF 0.798 B-11 0.042 5 1.5 0.84 192 steam 2.0 22.9 227 *Temperature: temperatures of raw materials for mortar formulation and working environments (room temperature) Types of cement in Table 9 are described below. Cement of Vietnam: PCB-40 manufactured by Nghi Son Cement Corporation Cement of Thai: Type 1 manufactured by The Siam Cement Public Company Ltd. Cement of Malaysia: OPC manufactured by Lafarge Malaysia Berhad Cement of Indonesia: OPC manufactured by PT Semen Indonesia (persero) Tbk Cement of China: 52.5 manufactured by Anhui Conch Cement Company Limited

(79) In Table 9, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(80) Further, in Table 9, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).

(81) Further, in Table 9, the compressive strength ratio is a relative value regarding each cement, when the compressive strength of Comparative Example was taken as 100%.

Example 5 and Comparative Example 5

(82) Mortar was prepared in the same manner as in Example 2 by changing the mortar formulation as shown in Table 10 and also changing the presteaming period and the period up to demolding as shown in Tables 11 and 12; and the fluidity and the strength right after demolding (indicated as Right after demolding in the tables) were evaluated. Results are shown in Tables 11 and 12. In Table 11, the strength exhibited 28 days later (indicated as 28 days later in the table) is also shown. The period up to demolding is a period from the addition of mixing water (W) to the removal of the hardened product from the mold. Further, 28-day strength is a strength measured 28 days after the addition of mixing water (W) after the process including demolding 24 hours after the addition of the mixing water (W) and curing in water in a constant-temperature water bath at 30 C. In the case of no steam in the table, curing was conducted at the setting temperature (30 C.) from the addition of mixing water (W) to the strength measurement (24 hours later)

(83) TABLE-US-00010 TABLE 10 W/C Unit amount (g/batch) (mass %) W C S 35 140 400 700

(84) TABLE-US-00011 TABLE 11 Compressive strength Component Component Right after (A) (B) (B)/ Molar Total Time demolding 28 days later Added Added [(A) ratio of added Pre- till Com- Com- amount amount + (B)/ amount Mor- steam- de- Meas- pressive Meas- pressive W/C (part (part (B)] naphtha- (part tar Curing ing mold- ured strength ured strength (mass by by (mass lene by flow con- time ing value ratio value ratio %) Type mass) Type mass) %) ring (%) mass) (mm) dition (hr.) (hr.) (MPa) (%) (MPa) (%) Com- 5-1 35 NSF 0.660 0 0.0 0.66 190 steam 3.0 7.0 21.7 100 37.1 100 par- ative Exam- ple Exam- 5-1 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 3.0 7.0 33.1 153 64.0 173 ple Com- 2-1 35 NSF 0.660 0 0.0 0.66 190 steam 2.0 6.0 12.9 100 27.5 100 par- ative Exam- ple Exam- 2-28 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 2.0 6.0 21.8 169 41.8 152 ple Com- 5-2 35 NSF 0.660 0 0.0 0.66 190 steam 1.0 5.0 9.7 100 32.9 100 par- ative Exam- ple Exam- 5-2 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 1.0 5.0 16.3 168 37.3 113 ple Com- 5-3 35 NSF 0.660 0 0.0 0.66 190 steam 0.5 4.5 8.7 100 37.9 100 par- ative Exam- ple Exam- 5-3 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 steam 0.5 4.5 15.8 182 40.1 106 ple Com- 5-4 35 NSF 0.660 0 0.0 0.66 190 no (24) 24.0 28.4 100 72.1 100 par- steam ative Exam- ple Com- 5-5 35 NSF 0.589 B-11 0.031 5 1.5 0.62 182 no (24) 24.0 29.6 104 75.2 104 par- steam ative Exam- ple

(85) TABLE-US-00012 TABLE 12 Com- Component Component pressive (A) (B) strength Added Added Molar Total Time (right Com- amount amount (B)/[(A) ratio of added Mor- Pre- till after pressive W/C (part (part + (B)/ amount tar Curing steaming de- de- strength (mass by by (B)] naphthalene (part by flow con- time molding molding) ratio %) Type mass) Type mass) (mass %) ring (%) mass) (mm) dition (hr.) (hr.) (MPa) (%) Com- 5-1 35 NSF 0.660 0 0.0 0.66 190 steam 3.0 7.0 21.7 100 parative Example Example 5-5 35 NSF 0.496 B-11 0.124 20 7.0 0.62 182 steam 3.0 7.0 35.4 163 Com- 2-1 35 NSF 0.660 0 0.0 0.66 190 steam 2.0 6.0 12.9 100 parative Example Example 5-6 35 NSF 0.496 B-11 0.124 20 7.0 0.62 190 steam 2.0 6.0 27.5 213 Com- 5-2 35 NSF 0.660 0 0.0 0.66 190 steam 1.0 5.0 9.7 100 parative Example Example 5-7 35 NSF 0.496 B-11 0.124 20 7.0 0.62 182 steam 1.0 5.0 17.6 181 Com- 5-3 35 NSF 0.660 0 0.0 0.66 190 steam 0.5 4.5 8.7 100 parative Example Example 5-8 35 NSF 0.496 B-11 0.124 20 7.0 0.62 182 steam 0.5 4.5 15.6 179 Com- 5-4 35 NSF 0.660 0 0.0 0.66 190 no (24) 24.0 28.4 100 parative steam Example Example 5-6 35 NSF 0.496 B-11 0.124 20 7.0 0.62 182 no (24) 24.0 29.4 104 steam

(86) In Tables 11 and 12, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(87) Further, in Tables 11 and 12, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).

(88) Further, in Tables 11 and 12, the compressive strength ratio is a relative value regarding each presteaming period, when the compressive strength of Comparative Example was taken as 100%.

(89) It is understood that, in the case of no steam curing, addition of components (A) and (B) in predetermined amounts hardly changes the compressive strength while in the case of steam curing, addition of components (A) and (B) in predetermined amounts increases the compressive strength. The same is true in the compressive strength after 28 days. In general, it is common knowledge to those skilled in the art that, when steam curing is conducted, 28-day strength is reduced in comparison with a case where steam curing is not conducted.

Example 6 and Comparative Example 6

(90) Mortar was prepared in the same manner as in Example 2 by replacing a portion of cement in the mortar formulation of Example 2 with fly ash, and the fluidity and the strength were evaluated. Replacement rates with fly ash are shown in Table 13. In Table 13, FA is an abbreviation for fly ash. As fly ash, fly ash original powder from China was used. Results are shown in Table 14.

(91) TABLE-US-00013 TABLE 13 Fly ash replacement W/(C + FA) Unit amount (g/batch) ratio (%) (mass %) W C FA S 0 35 140 400 0 700 10 35 140 360 40 700 20 35 140 320 80 700

(92) TABLE-US-00014 TABLE 14 Component Component (A) (B) Molar Total Com- Fly Added Added (B)/[(A) ratio of added Pre- Com- pressive ash amount amount + (B)/ amount Mortar Curing steaming pressive strength replacement (part by (part by (B)] naphthalene (part by flow con- time strength ratio ratio (%) Type mass) Type mass) (mass %) ring (%) mass) (mm) dition (hr.) (MPa) (%) Com- 6-1 0 NSF 0.600 0 0.0 0.60 180 steam 2.0 16.5 100 parative Example Example 6-1 0 NSF 0.570 B-19 0.030 5 1.3 0.60 188 steam 2.0 26.8 162 Com- 6-2 10 NSF 0.600 0 0.0 0.60 166 steam 2.0 14.9 100 parative Example Example 6-2 10 NSF 0.570 B-19 0.030 5 1.3 0.60 176 steam 2.0 19.6 132 Com- 6-3 20 NSF 0.600 0 0.0 0.60 173 steam 2.0 12.2 100 parative Example Example 6-3 20 NSF 0.570 B-19 0.030 5 1.3 0.60 173 steam 2.0 14.5 119

(93) In Table 14, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(94) Further, in Table 14, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).

(95) Further, in Table 14, the compressive strength ratio is a relative value regarding each fly ash replacement rate, when the compressive strength of Comparative Example was taken as 100%.

(96) From the results of Table 14, it is understood that even when a portion of cement is replaced with fly ash, the present invention enables the strength improvement.

Example 7 and Comparative Example 7

(97) (1) Mortar Formulation

(98) Mortar formulation is shown in Table 15.

(99) TABLE-US-00015 TABLE 15 W/C Unit amount (g/batch) (mass %) W C S 23.8 142.8 600 857

(100) Components in the table are as follows.

(101) W: water from public water supply system in Wakayama

(102) C: PCT-40 manufactured by Nghi Son Cement Corporation (Vietnam)

(103) S: fine aggregate (pit sand from Joyo area, particles having a particle size of 3.5 mm or more were removed)

(104) W in Table 15 contains none of components selected from components (A), (B) and (C) used in Table 17.

(105) Components (A), (B) and (C) in Table 17 are as follows.

(106) [Component (A)]

(107) NSF: sodium salt of a formaldehyde naphthalenesulfonate condensate, weight average molecular weight: 15000

(108) This NSF was prepared based on Example of JP-A 48-11737.

(109) [Component (B)]

(110) Components (B) shown in Table 16 were used.

(111) [Component (C)]

(112) PCE (A): polycarboxylic acid-based dispersant, AQUPOL MAR502(S) manufactured by AK Chemtech Co., Ltd. PCE (B): methacrylic acid/methoxy polyethylene glycol (23) methacrylate=73/27 (molar ratio), prepared based on Production Example 11 of JP-A 8-12397 PCE (C): acrylic acid/methoxy polyethylene glycol (23) acrylate=77/23 (molar ratio), prepared based on Production Example 11 of JP-A 8-12397 PCE (D): polycarboxylic acid-based dispersant, AQUALOC HW-80 manufactured by Nippon Shokubai Co., Ltd.
(2) Method for Preparing Mortar

(113) Temperatures of raw materials for mortar formulation and the temperature of working environment (room temperature) were both set to 30 C.

(114) Into a mortar mixer (universal mixing stirrer, model: 5DM-03- manufactured by Dalton Corporation), a cement (C) and a fine aggregate (S) were fed and dry-mixed for 10 seconds at a low speed rotation (63 rpm) of the mortar mixer, and the mixing water (W) containing components (A), (B) and (C), an antifoaming agent, and water (W) at 30 C. was added. Then, the mixture was subjected to main kneading for 180 seconds at a low speed rotation (63 rpm) of the mortar mixer, so that a mortar was prepared.

(115) As the antifoaming agent, Foamlex 797 (manufactured by Nicca Chemical Co., Ltd.) was added in an amount of 3 mass % relative to component (B).

(116) (3) Fluidity

(117) In accordance with the test method of JIS R 5201, the flow of the prepared mortar was measured. Results are shown in Table 17.

(118) In Examples, components (A) to (C) were added in total in an amount of 0.60 parts by mass relative to 100 parts by mass of cement.

(119) (4) Strength

(120) The mortar was hardened by a production method including steam curing, and the strength of the hardened product of the obtained mortar was tested in accordance with JIS A 1108 Method of test for compressive strength of concrete.

(121) Steam curing for obtaining the hardened product was conducted after a predetermined period of presteaming. The presteaming was conducted at 30 C. for 3 hours.

(122) Steam curing was carried out at a humidity setting of 100% by use of a thermo-hygrostat PR-3J manufactured by Espec Corporation.

(123) Temperature rise for steam curing was conducted for 45 minutes from 30 C. to 75 C., which were setting temperatures for the thermo-hygrostat. Steam curing was conducted for 2.5 hours at a constant temperature of 75 C., which was a setting temperature for the thermo-hygrostat. Temperature drop for steam curing was conducted for 45 minutes from 75 C. to 30 C., which were setting temperatures for the thermo-hygrostat. Immediately after the setting temperature of the thermo-hygrostat reached 30 C., the strength was measured.

(124) TABLE-US-00016 TABLE 16 Component (B) Mark Type Carbon No.* B-27 Polyoxyethylene (50) stearyl ether 18 B-28 Polyoxyethylene (19) lauryl ether ammonium sulfate 12 B-29 Polyoxyethylene (20) stearyl amine ether 18

(125) TABLE-US-00017 TABLE 17 Component Component Component (B)/ Molar Other additive (A) (B) (C) [(A) ratio of Total Added Com- Added Added Added + (B)/ added amount Mor- Com- pressive amount amount amount (B)] naphtha- amount* (part tar pressive strength (part by (part by (part by (mass lene (part by by flow strength ratio Type mass) Type mass) Type mass) %) ring (%) mass) Type mass) (mm) (MPa) (%) Com- 7-1 NSF 1.400 0 0.0 1.40 157 27.1 100 par- 7-2 NSF 0.180 PCE(A) 0.300 0.48 not kneable, thus ative not measureable Exam- ples Exam- 7-1 NSF 0.180 B-27 0.120 PCE(A) 0.300 40 6.5 0.60 235 49.1 181 ples 7-2 NSF 0.180 B-27 0.060 PCE(A) 0.300 20 11.2 0.60 198 50.2 185 B-28 0.060 7-3 NSF 0.180 B-29 0.120 PCE(A) 0.300 40 14.1 0.60 169 49.4 182 7-4 NSF 0.180 B-29 0.120 PCE(B) 0.300 40 14.1 0.60 141 44.6 164 7-5 NSF 0.180 B-29 0.120 PCE(C) 0.300 40 14.1 0.60 99 50.4 186 7-6 NSF 0.180 B-29 0.120 PCE(D) 0.300 40 14.1 0.60 105 51.9 192 7-7 NSF 0.180 B-29 0.090 PCE(A) 0.300 30 9.0 0.60 194 39.6 146 7-8 NSF 0.180 B-29 0.090 PCE(A) 0.300 30 9.0 0.60 glycerin 0.05 127 41.4 153 7-9 NSF 0.180 B-29 0.090 PCE(A) 0.300 30 9.0 0.60 glycerin 0.05 145 45.4 168 EDTA-4Na 0.02 7-10 NSF 0.210 B-29 0.090 PCE(A) 0.300 30 9.0 0.60 N-methyl- 0.02 166 57.4 212 diethanolamine

(126) In Table 17, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(127) Further, in Table 17, the total added amount is an added amount of the total of components (A), (B) and (C) in terms of solid content relative to 100 parts by mass of cement (C).

(128) Further, in Table 17, the compressive strength ratio is a relative value when the compressive strength of Comparative Example 7-1 was taken as 100%.

(129) When NSF as component (A) and PCE as component (C) are used in combination, the viscosity increases if component (B) is not added. Therefore, as shown in Comparative Example 7-2, even combined use of components (A) and (C) did not develop the fluidity of the hydraulic composition, without component (B).

Example 8 and Comparative Example 8

(130) Concrete for centrifugal molding was prepared in the same manner as in Example 1 according to the concrete formulation of Table 18 by using components (A) and (B) in Table 19, and the moldability for centrifugal molding and the compressive strength were evaluated in the same manner as in Example 1. Results are shown in Table 19.

(131) TABLE-US-00018 TABLE 18 W/(C + P) Unit amount (kg/m.sup.3) (mass %) W C P S G 18.7 125 600 65 595 1100

(132) TABLE-US-00019 TABLE 19 Component (A) Component (B) Total Molar Added Added added (B)/[(A) ratio of amount amount amount + (B)/ Compressive (part by (part by (part by (B)] naphthalene strength Type mass) Type mass) mass) (mass %) ring (%) (MPa) Moldability Exam- 8-1 NSF 0.98 B-19 0.02 1.00 2.0 0.5 130 A ple 8-2 NSF 0.85 B-19 0.05 0.90 5.6 1.4 131 AA 8-3 NSF 0.72 B-19 0.08 0.80 10.0 2.7 133 AA 8-4 NSF 0.66 B-19 0.17 0.70 20.5 6.3 136 AA 8-5 NSF 0.49 B-19 0.21 0.70 30.0 10.5 138 AA 8-6 NSF 0.66 B-20 0.17 0.70 20.5 5.0 137 AA 8-7 NSF 0.66 B-21 0.17 0.70 20.5 3.6 134 AA 8-8 NSF 0.66 B-22 0.17 0.65 20.5 1.9 136 AA 8-9 NSF 0.98 B-9 0.02 1.00 2.0 0.3 130 A 8-10 NSF 0.85 B-13 0.05 0.90 5.6 1.1 131 AA 8-11 NSF 0.66 B-13 0.17 0.80 20.5 4.9 133 AA Com- 8-1 NSF 1.5 1.50 69.4 C parative 8-2 NSF 2.5 2.50 124 AA Exam- ples

(133) In Table 19, the added amount is an added amount of each component in terms of solid content relative to 100 parts by mass of cement (C).

(134) Further, in Table 19, the total added amount is an added amount of the total of components (A) and (B) in terms of solid content relative to 100 parts by mass of cement (C).