JPH08165157A - Cement additive composition - Google Patents

Abstract

PURPOSE: To suppress the variation of air content with time and improve water- reducing property, etc., by compounding a hydrolyzate (salt) of a specific copolymer, a polyoxyalkylene(PA) compound and a polyoxyethylene(PE) compound. CONSTITUTION: This cement additive composition is produced by compounding 100 pts.wt. of a copolymer produced by copolymerizing a PA compound of formula I (R<1> is a 2-5C alkenyl; A<1> O is a 2-4C PA and 50-100mol% of the A<1> O is PE; R<2> is a 1-18C hydrocarbon group; (a) is 1-200) and maleic anhydride at a molar ratio of 3/7 to 7/3 or its hydrolyzate (salt) with 0.01-5 pts.wt. of a PA compound of formula II (Z is a residue produced by removing hydroxyl groups from a compound containing 2-8 hydroxyl groups; A<2-5> O are each oxypropylene or oxybutylene; R<3-4> are each H, a 1-22C hydrocarbon group or an acyl; (b), (d), (e) and (g) are each 0-100; (c) and (f) are each 0-20; (h) and (i) are each 0-8; h+i corresponds to the number of hydroxyl groups of Z) and 0.1-10 pts. wt. of a PE compound of formula III (R<5> is a 8-22C hydrocarbon group; X is an alkali metal, ammonium or an organic amine; (j) is 15-100).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel cement additive composition. More specifically, the present invention has a high water-reducing property and a high slump loss preventive property, appropriately adjusts the amount of air entrained during concrete mixing, and has little change in the amount of air over time. Regarding

[0002]

2. Description of the Related Art Conventionally, compounds such as naphthalene sulfonic acid type, melamine sulfonic acid type, lignin sulfonic acid type and polycarboxylic acid type have been used as cement admixtures. In recent years, the demand for high strength of concrete has increased, and it has become necessary to reduce the amount of water (unit water amount) in the concrete composition. However, the admixture for cement described above, although having the effect of reducing the amount of unit water in the concrete composition, has the drawback that it is not possible to improve the so-called slump loss, which is a decrease in the fluidity of the concrete composition that occurs over time. Had. In order to prevent this slump loss, a method of adding a large amount of a polycarboxylic acid compound to the concrete composition, a method of using a polycarboxylic acid copolymer having a sustained release effect, or an admixture thereof is used. Methods such as split addition and post-addition have been proposed. However, in these methods, although the prevention of slump loss is improved, air entrainment during mixing of the concrete composition is increased,
Therefore, there are problems that the strength of the cured product is reduced, the appearance of the molded product is deteriorated, and the freeze-thaw resistance is poor. On the other hand, a method of adjusting the amount of air by using a polycarboxylic acid compound whose molecular weight has been adjusted by fractionation, and also using an antifoaming agent or an antifoaming agent and a foaming agent together with an admixture Has proposed a method of adjusting the amount of air, but the amount of air immediately after kneading can be adjusted, but in each case, the change in the amount of air over time is large, and it was difficult to introduce air stably. Also,
In practical use, the admixture with an antifoaming agent is generally poor in storage stability when it is used as a dilute aqueous solution. That is, since the defoamer component causes a separation phenomenon in a dilute aqueous solution, the quality of concrete may become unstable when measured in a fresh concrete plant. Therefore, a special device was required for the admixture tank, such as re-stirring before weighing.
As described above, in the conventional technology, it is extremely difficult to stably introduce the amount of air required for achieving high water reduction and high slump loss prevention, further excellent aesthetics, and obtaining the required durability of concrete. Met.

[0003]

Under the circumstances, the present invention has high water reducing property and high slump loss preventing property, and appropriately adjusts the amount of air entrained during concrete mixing, Moreover, the purpose of the present invention is to provide an additive composition for cement, which has a small change in the amount of air over time.

[0004]

[Means for Solving the Problems] As a result of intensive studies to develop a cement additive composition having the above-mentioned preferable properties, the present inventors have identified a specific copolymer and a defoaming effect. A polyoxyalkylene compound of, and a dispersion of
A mixture of a specific polyoxyethylene compound having an emulsifying and solubilizing effect in a specific ratio exerts a high water reducing effect and a high slump loss preventing effect when added to a concrete composition, and adjusts the amount of air entrained. It was found that the above was possible and there was little change in the air amount over time, and the present invention was completed based on this finding. That is, the present invention provides (1) (A) (a) general formula [1] R ¹ O (A ¹ O) _a R ² ... [1] (wherein R ¹ is an alkenyl group having 2 to 5 carbon atoms, A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms and 50 to 100 thereof
Mol% is an oxyethylene group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and a is 1 to 200. (B) with respect to 100 parts by weight of a copolymer of a polyoxyalkylene compound represented by the formula (4) and (b) maleic anhydride, a hydrolyzate or a salt of the hydrolyzate thereof, (B) the general formula [2]

Embedded image (However, Z is a residue excluding the hydroxyl group of the compound having 2 to 8 hydroxyl groups, A ² O, A ³ O, A ⁴ O and A ⁵ O are each an oxypropylene group or an oxybutylene group,
They may be the same or different from each other, or 1
And R ³ and R ⁴ are hydrogen, a hydrocarbon group or an acyl group having 1 to 22 carbon atoms, b, d, e and g are 0 to 100, and c and f are 0 to 0, respectively. 20, h
And i are 0 to 8, and the sum of h and i corresponds to the number of hydroxyl groups possessed by Z. Here, b, c, d, e, f and g are never 0 at the same time. 0.01 to 5 parts by weight of a polyoxyalkylene compound represented by the formula (4), and (C) the general formula [3] R ⁵ O (C ₂ H ₄ O) _j SO ₃ X ... [3] (provided that R ⁵ Is a hydrocarbon group having 8 to 22 carbon atoms, X is an alkali metal, an ammonium group or an organic amine group, and j is 15 to 100). An additive composition for cement containing as an active ingredient, and (2) the additive for cement according to item (1), wherein j of the polyoxyethylene compound represented by the general formula [3] is 20 to 80. An agent composition is provided.

The present invention will be described in detail below. In the cement additive composition of the present invention, the copolymer of the component (A) used as an active ingredient is (a) a general formula [1] R ¹ O (A ¹ O) _a R ² ... [1] It is a copolymer of the represented polyoxyalkylene compound and (b) maleic anhydride, its hydrolyzate or a salt of the hydrolyzate. In the above general formula [1], R ¹ is an alkenyl group having 2 to 5 carbon atoms, and specific examples thereof include vinyl group, allyl group, isopropenyl group, methallyl group, 3-
Examples thereof include a butenyl group, 4-pentenyl group, 3-methyl-3 butenyl group and the like. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and 50 mol% or more thereof is an oxyethylene group. Specific examples of the oxyalkylene group other than the oxyethylene group include, for example, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, and at least 50 mol% or more of the oxyalkylene groups are oxyethylene groups. For example, it may be a copolymer with the above-mentioned other oxyalkylene group. If the oxyethylene group content is less than 50 mol%, the water solubility may be insufficient and a high water reducing effect may not be exhibited. Further, a is 1 to 200. a is 200
If it exceeds, the viscosity becomes high, which may make the production difficult. Further, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group and an isoamyl group. , Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Tetradecyl group, hexadecyl group, octadecyl group, oleyl group, phenyl group, benzyl group, cresyl group, butylphenyl group, octylphenyl group, nonylphenol group, saturated hydrocarbon group such as naphthyl group, unsaturated hydrocarbon group, aromatic carbon group Examples thereof include a hydrogen group and a substituted aromatic hydrocarbon group.

The copolymer of the component (A) can be obtained by copolymerizing the polyoxyalkylene compound represented by the general formula [1] of the component (a) with maleic anhydride. The reaction ratio of the polyoxyalkylene compound represented by the general formula [1] of the component (a) and the maleic anhydride of the component (b) is preferably in the range of 3/7 to 7/3, and particularly 1 / 1 is preferable. Further, at the time of copolymerization, a copolymerizable monomer such as styrene, (meth) acrylic acid, (meth) acrylic acid ester, vinyl acetate or the like can be added and copolymerized. Further, the above copolymer is
It can be used as a hydrolyzate, that is, an acid-type copolymer, or a salt of a hydrolyzate, that is, a salt-type copolymer. The acid-type copolymer means a maleic anhydride unit in the copolymer of the above polyoxyalkylene compound and maleic anhydride is converted into a free maleic acid unit, and
The salt-type copolymer means that the maleic acid unit forms a salt. The acid-type copolymer can be produced by copolymerizing the polyoxyalkylene compound as the component (a) and the maleic anhydride as the component (b) and then hydrolyzing it.
Alternatively, it can be produced by copolymerizing the polyoxyalkylene compound and maleic acid. The salt-type copolymer can be produced by neutralizing the acid-type copolymer obtained as described above, or can be produced by copolymerizing the polyoxyalkylene compound and the maleate salt. It is also possible to do so. As the salt-type copolymer,
Examples thereof include alkali metal salts such as lithium salts, sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; ammonium salts, and organic amine salts. Examples of the organic amine salt include methylamine salt, ethylamine salt, propylamine salt, hexylamine salt, octylamine salt, 2-ethylhexylamine salt, decylamine salt, dodecylamine salt, tridecylamine salt, tetradecylamine salt, hexadecyl salt. Aliphatic amine salts such as amine salts, isohexadecylamine salts, octadecylamine salts, isooctadecylamine salts, octyldodecylamine salts, docosylamine salts, decyltetradecylamine salts, dimethylamine salts, trimethylamine salts, triethylamine salts; ethylenediamine salts , Aliphatic polyamine salts such as tetramethylenediamine salt, dodecyl-propylenediamine salt, tetradecyl-propylenediamine salt, tetraethylenepentamine salt, pentaethylenehexamine salt; monoethanol Min salt, diethanolamine salt, triethanolamine salt,
Alkanolamine salts such as monoisopropanolamine salt, diisopropanolamine salt and triisopropanolamine salt, and salts of these alkylene oxide adducts; alicyclic carbon hydrogen amine salts such as cyclohexylamine salts, aniline salts, toluidine salts and the like. Examples include aromatic monoamine salts. Of these, alkali metal salts, ammonium salts and alkanolamine salts are particularly preferable. These (A) component copolymers are
A maleic anhydride copolymer, a hydrolyzate thereof or a salt of a hydrolyzate thereof can be used alone, and two different maleic anhydride copolymers, different hydrolysates or salts of different hydrolysates can be used. The above can be used in combination, and further, two or more kinds can be used in combination from the copolymer of maleic anhydride, its hydrolyzate and salts of the hydrolyzate.

In the cement additive composition of the present invention, the component (B) used as an active ingredient is represented by the general formula [2]

Embedded image It is a polyoxyalkylene compound represented by. In the general formula [2], Z is a residue excluding a hydroxyl group of a compound having 2 to 8 hydroxyl groups. Examples of the compound having 2 to 8 hydroxyl groups include polyhydric phenols such as catechol, resorcin, hydroquinone and phloroglucin; ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, dodecylene glycol, octadecylene glycol. , Neopentyl glycol, styrene glycol, glycerin, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentanetriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbide, sorbitol- Glycerin condensate, adonitol,
Polyhydric alcohols such as arabitol, xylitol and mannitol; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose,
Mannose, sorbose, cellobiose, maltose,
Examples thereof include sugars such as isomaltose, trehalose, and sucrose; and partial etherified products and partially esterified products thereof. A ² O, A ³ O, A ⁴ O and A ⁵ O are an oxypropylene group or an oxybutylene group, which may be the same or different from each other, and are one type or two types. May be. That is, (A ² O) _b , (A ³ O) _d , (A ⁴ O) _e and (A ⁵ O)
Each of _g may have a structure in which one of propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide is added alone, or a structure in which two or more of these are added.

R ³ and R ⁴ are each hydrogen, a hydrocarbon group having 1 to 22 carbon atoms or an acyl group. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t
-Butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexa group Decyl group, heptadecyl group, octadecyl group, isooctadecyl group, nonadecyl group, eicosyl group, docosyl group, oleyl group, octyldodecyl group, behenyl group, cyclohexyl group, benzyl group, cresyl group, butylphenyl group, dibutylphenyl group, octyl group Examples thereof include saturated hydrocarbon groups such as phenyl group, nonylphenyl group and dodecylphenyl group, unsaturated hydrocarbon groups, alicyclic hydrocarbon groups, aromatic groups and substituted aromatic groups. Further, as the acyl group, formic acid, acetic acid, propionic acid,
Butyric acid, isobutyric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, undecylenic acid, lauric acid, myristic acid, margaric acid, stearic acid, arachidic acid, behenic acid, palmitoleic acid, oleic acid,
Examples thereof include linear saturated acyl groups, branched saturated acyl groups, unsaturated acyl groups and aromatic acyl groups derived from linoleic acid, linolenic acid, erucic acid, isopartic acid, isostearic acid, benzoic acid and the like. In the present invention, when the hydrocarbon group or the acyl group represented by R ³ or R ⁴ has more than 22 carbon atoms, the hydrophobicity becomes too large and the defoaming property deteriorates. Particularly preferred hydrocarbon group has 12 to 12 carbon atoms.
18 saturated or unsaturated hydrocarbon groups.
Further, b, d, e and g are each 0 to 100. When b, d, e and g exceed 100, the hydrophobicity becomes too large and the defoaming property deteriorates. c and f are 0-2
0. When c and f exceed 20, hydrophilicity becomes too large and the defoaming effect decreases. h and i are 0 to 8, and the sum of h and i corresponds to the total number of hydroxyl groups possessed by Z. The value of h (b + c + d) + i (e + f + g) is 1 or more, and particularly preferably 1 to 300. If this value exceeds 300, the viscosity becomes high and the production becomes difficult. In the present invention, the method for producing the polyoxyalkylene compound as the component (B) is not particularly limited,
For example, propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide is added to a compound having 2 to 8 hydroxyl groups, ethylene oxide is further added, and then propylene oxide, 1,2-butylene oxide or It can be obtained by adding 2,3-butylene oxide, and further by substituting a part or all of the hydrogen atoms of the free hydroxyl group with a hydrocarbon group or an acyl group by a known method.

In the cement additive composition of the present invention, the component (C) used as an active ingredient is represented by the general formula [3] R ⁵ O (C ₂ H ₄ O) _j SO ₃ X ... [3] The polyoxyethylene compound is used. In the general formula [3], R ⁵ is a hydrocarbon group having 8 to 22 carbon atoms, and examples of the hydrocarbon group include an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, isooctadecyl group, nonadecyl group, eicosyl group, docosyl group, oleyl group, octyldecyl group, behenyl group, cresyl group, Examples thereof include saturated hydrocarbon groups such as butylphenyl group, dibutylphenyl group, octylphenyl group, nonylphenyl group and dodecylphenyl group, unsaturated hydrocarbon groups, aromatic groups and substituted aromatic groups. X is an alkali metal, ammonium group, or organic amine group. Examples of the alkali metal include metals such as lithium, sodium and potassium. As the organic amine group, a monomethylammonium group, a dimethylammonium group, a trimethylammonium group, a monoethylammonium group,
Diethyl ammonium group, triethyl ammonium group,
Monopropylammonium group, dipropylammonium group, tripropylammonium group, monobutylammonium group, dibutylammonium group, tributylammonium group, hexylammonium group, cyclohexylammonium group, anilinium group, pyridinium group, N-methylpyridinium group, etc. Examples thereof include primary ammonium group, secondary ammonium group, tertiary ammonium group, and heterocyclic ammonium group. Of these, alkali metal and ammonium groups are particularly preferable. Also, j
Is 15 to 100, preferably 20 to 80. When j is less than 15, the foaming action becomes strong, so that the amount of air increases and relatively large bubbles remain on the concrete surface, which is not preferable. On the other hand, when it exceeds 100, the hydrophilicity becomes too large and the surface activity is lowered. In the present invention, the method for producing the polyoxyethylene compound as the component (C) is not particularly limited, but it can be obtained, for example, by adding ethylene oxide to a hydroxyl group-containing compound and then reacting it with chlorosulfonic acid. Further, by neutralizing with an alkali compound, the terminal can be made into a corresponding alkali metal.
Further, the terminal can be converted to an ammonium group or an organic amine group by a reaction with ammonium hydroxide or the like or a reaction with an organic amine. In the present invention, a,
b, c, d, e, f, g, h, i and j are 0 or an integer as one molecule of the compound, but the component (A),
Since the components (B) and (C) are usually mixed with compounds having different molecular weights, a to j are numerical values represented by average values, and are not necessarily integers.

In the additive composition for cement of the present invention, the polyoxyalkylene compound of the component (B) is added to 100 parts by weight of the copolymer of the component (A), its hydrolyzate or a salt of the hydrolyzate. 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, and more preferably 0.03 to 1 part by weight.
Add parts by weight. The compounding amount of the polyoxyalkylene compound as the component (B) is 0.1 with respect to 100 parts by weight of the component (A).
If it is less than 01 parts by weight, the defoaming effect cannot be sufficiently exhibited. Further, even if the blending amount of the polyoxyalkylene compound as the component (B) exceeds 5 parts by weight with respect to 100 parts by weight of the component (A), a remarkable improvement in the defoaming effect commensurate with the increase in the blending amount is not observed. . In the cement additive composition of the present invention, the polyoxyethylene compound of the component (C) is added to 100 parts by weight of the copolymer of the component (A), a hydrolyzate thereof or a salt of the hydrolyzate. The amount is 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of the polyoxyethylene compound as the component (C) is less than 0.1 part by weight relative to 100 parts by weight of the component (A), the polyoxyalkylene compound as the component (B) is sufficiently dispersed or emulsion-stabilized. Cannot be solubilized or solubilized. Further, when the blending amount of the polyoxyethylene compound as the component (C) exceeds 10 parts by weight with respect to 100 parts by weight of the component (A), the foaming action becomes too large, and the entrained air amount in the concrete composition is increased. It may become too large. In the additive composition for cement of the present invention, the amounts of the component (B) and the component (C) are
It can be appropriately selected and used according to each performance and usage amount. The cement additive composition of the present invention,
Usually, it is added in an amount of 0.01 to 3% by weight, preferably 0.04 to 1% by weight, based on the amount of cement. As the cement here, ordinary Portland cement, early strength Portland cement, super early strength Portland cement,
Moderate heat Portland cement, Portland cement such as sulfate resistant Portland cement; mixed cement such as blast furnace cement, silica cement, fly ash cement; or mixture of these cement and blast furnace slag, silica fume, fly ash, limestone powder, gypsum, etc. Cement in which materials are combined; and further, special cements such as oil well cement, high sulfate slag cement, alumina cement, magnesium cement, and acid resistant cement can be mentioned. These cements can be used alone or in combination of two or more, if necessary. When the additive amount of the cement additive composition of the present invention is less than 0.01% by weight relative to the cement, it is an effect of the cement additive composition of the present invention that high water reduction and high slump loss prevention are achieved. Sex is not fully exerted. Further, when the additive amount of the cement additive composition of the present invention exceeds 3% by weight with respect to the cement, the effect of the cement additive composition of the present invention is exhibited, but work is delayed due to delay of setting or the like. May deteriorate. Cement additive composition of the present invention, within the range that does not impair the performance, naphthalene sulfonic acid formalin condensate salt, melamine sulfonic acid formaldehyde condensate salt, other cement dispersants such as polycarboxylic acid compounds, or Antifoam agent, air entrainment agent,
It can be used in combination with a rust preventive agent, a setting accelerator, a setting retarder and the like.

[0011]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Examples 1 to 14 In this example, as the component (A), a copolymer of the (a) polyoxyalkylene compound and the (b) maleic acid derivative shown in Table 1 was used. As the component (B), the polyoxyalkylene compound shown in Table 2 was used. Further, the polyoxyethylene compounds shown in Table 3 were used as the component (C). The components were mixed in the proportions shown in Table 4 to prepare a cement additive composition. Tests with concrete were carried out using these additive compositions for cement.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

[0015]

[Table 4]

The composition and test conditions are shown below. Composition water 166kg / m³ Cement 450kg / m³  Sand 713kg / m³ Crushed stone 999kg / m³ Additive composition Amount shown in Table 5 Water / cement ratio 37.0% by weight Fine aggregate ratio 42.0% by weight Take each of the above components in a forced mixing mixer and mix for 2 minutes.
After that, it was taken out, and the slump and the air amount were measured. It
Transfer to a tilting mixer and mix at 2 revolutions per minute for 30 minutes
After 60 minutes, the slump and the amount of air were measured. Also
The setting time and compressive strength were measured. The test method is as follows
It is as follows. -Slump: Compliant with JIS A 1101-Air amount: Compliant with JIS A 1128-Coagulation time: Compliant with JIS A 6204, Annex 1-Compressive strength: Compliant with JIS A 1108 Table 5 shows the results obtained.

[0017]

[Table 5]

Note 1) Evaluation of surface condition ◎: Small bubbles, no large bubble traces are observed ○: Large bubble traces are slightly visible at the bottom △: Large bubble traces are slightly visible ×: Large bubble traces are all Seen in Example 15 After the additive composition used in Example 5 was prepared, it was allowed to stand still for 1 month, and the upper layer was sampled without re-stirring. The test was repeated. The results are shown in Table 5. Example 16 After the additive composition used in Example 5 was prepared, it was allowed to stand still for 1 month and the lower layer was sampled without re-stirring, and the same test as in Examples 1 to 14 was repeated. It was The results are shown in Table 5. Comparative Examples 1 to 6 Tests similar to those in Examples 1 to 14 were performed using the compounds shown below. Table 5 shows the results. Comparative Example 1 With respect to 100 parts by weight of a monoammonium salt of a copolymer of styrene and maleic anhydride, 0.20 part by weight of the polyoxyalkylene compound B1 shown in Table 2 and the polyoxyethylene compound C4 shown in Table 3 were added. Added 0.30 parts by weight. Comparative Example 2 With respect to 100 parts by weight of the monosodium salt of a copolymer of pentene and maleic anhydride, 0.20 parts by weight of the polyoxyalkylene compound B1 shown in Table 2 and the third
Addition of 0.30 parts by weight of the polyoxyethylene compound C4 shown in the table. Comparative Example 3 To 100 parts by weight of the copolymer A2 shown in Table 2, 0.10 parts by weight of the polyoxyalkylene compound B1 shown in Table 2 and 0.30 parts by weight of sodium dodecylbenzenesulfonate were added. . Comparative Example 4 0.10 parts by weight of the polyoxyalkylene compound B1 shown in Table 2 and 100 parts by weight of the copolymer A2 shown in Table 2 and polyoxyethylene (ethylene oxide addition mole number 3) nonylphenyl ether sulfuric acid Addition of 0.30 parts by weight of sodium ester. Comparative Example 5 Only copolymer A2 shown in Table 1. Comparative Example 6 To 100 parts by weight of the copolymer A2 shown in Table 1, 0.10 parts by weight of the polyoxyalkylene compound B1 shown in Table 2 was added, and the mixture was allowed to stand and stored for 1 month. Sampled from the upper layer without re-stirring. Comparative Example 7 0.10 parts by weight of the polyoxyalkylene compound B1 shown in Table 2 was added to 100 parts by weight of the copolymer A2 shown in Table 1, and the mixture was allowed to stand still for 1 month. Sampled from the lower layer without re-stirring. From the results of Examples 1 to 14 in Table 5, the samples containing the additive composition for cement of the present invention were mixed with each other immediately after mixing and at 60%.
The slump difference after a minute is small, and the slump loss is small.
In addition, the change in the air amount is small, and the difference in the air amount immediately after kneading and after 60 minutes is small. In the setting time test, both the initial and final times were normal and no abnormal setting was observed. Furthermore, the compressive strengths all show good values. Regarding the surface condition, there are 4 cases in which a large bubble trace is slightly seen in the lower part, but in the other 10 cases, the bubble is small and no large bubble trace is observed. Example 15 in Table 5 is one in which the additive composition of Example 5 was prepared, and then the mixture was allowed to stand for one month and stored, and the upper layer was sampled without re-stirring. Is an example in which after the additive composition of Example 5 was prepared, it was allowed to stand for one month and stored, and the lower layer was sampled without re-stirring. Good results that are almost the same as those of No. 5 are obtained. From these results, it can be seen that the additive composition for cement of the present invention is stable even after being left for one month without any change in quality, and the components are not separated. Comparative Example 1 is an example in which an ammonium salt of a copolymer of styrene and maleic anhydride is used in place of the component (A) of the composition of the present invention, and Comparative Example 2 is ( This is an example of using a sodium salt of a copolymer of pentene and maleic anhydride instead of the component A). In both cases, the slump loss is large, the change in the amount of air is slightly large, and the appearance of slightly large bubbles is small. Seen throughout. Comparative Example 3 is an example in which sodium dodecylbenzenesulfonate is used instead of the component (C) of the present invention, and Comparative Example 4 is oxyethylene added in place of the component (C) of the present invention. This is an example of using a polyoxyethylene compound with a small number of moles of the group, but in both cases, the foaming action is too strong and the stability of the air amount is poor, the compressive strength is a little low, and a large bubble trace is seen throughout the appearance. Inferior in terms of quality. Comparative Example 5 uses only the component (A) of the present invention,
This is an example in which the components (B) and (C) were not used, but the component (A) alone had a large amount of air, the stability of the amount of air was slightly inferior, and large air bubbles were slightly observed on the entire surface.
Comparative Example 6 and Comparative Example 7 were prepared by preparing a composition consisting of the component (A) and the component (B) excluding the component (C) of the present invention, and then storing the composition for 1 month without statically stirring. In this example, samples obtained by sampling the upper layer and the lower layer are used. Comparative Example 6 using the upper layer has a large defoaming effect, and Comparative Example 7 using the lower layer has a small defoaming effect and does not contain the component (C). It can be seen that the composition is unstable and the additive composition separates and the composition changes above and below in the container when stored for a long time.

[0019]

The cement additive composition of the present invention is effective when a specific polycarboxylic acid type copolymer, a specific polyoxyalkylene compound and a specific polyoxyethylene compound are mixed in a specific ratio. By using it as a component, it exerts a high water reducing effect and a high slump loss preventing effect when used in concrete, the amount of air entrained can be adjusted, and the change in the amount of air over time is small. Furthermore, even after the composition is stored in a stationary state for a long period of time, the composition does not separate, and the composition can be used without re-stirring, and exhibits excellent performance as in the preparation.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 65/26 NQN C08L 35/00 LHS 71/02 LQE // C04B 28/02 (C04B 28/02 24:32 A 24:26 H 24:02) 103: 32

Claims (2)

[Claims] 1. (A) (a) General formula [1] R ¹ O (A ¹ O) _a R ² ... [1] (wherein R ¹ is an alkenyl group having 2 to 5 carbon atoms, A ¹ O is 50 to 100 of an oxyalkylene group having 2 to 4 carbon atoms
Mol% is an oxyethylene group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and a is 1 to 200. )) A copolymer of a polyoxyalkylene compound represented by the formula (b) and (b) maleic anhydride, or a hydrolyzate thereof or 100 parts by weight of a salt of the hydrolyzate, (B) the general formula [2] (However, Z is a residue excluding the hydroxyl group of the compound having 2 to 8 hydroxyl groups, A ² O, A ³ O, A ⁴ O and A ⁵ O are each an oxypropylene group or an oxybutylene group,
They may be the same or different from each other, or 1
And R ³ and R ⁴ are hydrogen, a hydrocarbon group or an acyl group having 1 to 22 carbon atoms, b, d, e and g are 0 to 100, and c and f are 0 to 0, respectively. 20, h
And i are 0 to 8, and the sum of h and i corresponds to the number of hydroxyl groups possessed by Z. Here, b, c, d, e, f and g are never 0 at the same time. 0.01 to 5 parts by weight of a polyoxyalkylene compound represented by the formula (4), and (C) the general formula [3] R ⁵ O (C ₂ H ₄ O) _j SO ₃ X ... [3] (provided that R ⁵ Is a hydrocarbon group having 8 to 22 carbon atoms, X is an alkali metal, an ammonium group or an organic amine group, and j is 15 to 100). An additive composition for cement, containing as an active ingredient. 2. The additive composition for cement according to claim 1, wherein j of the polyoxyethylene compound represented by the general formula [3] is 20 to 80.