JPH10158045A - Cement admixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cement admixture which shows an excellent dispersion effect and slump holding effect without causing retardation in curing and which shows significant resistance against separation of materials. SOLUTION: The admixture consists of (A) a vinyl triazine expressed by the formula or its deriv., (B) an ester of polyoxyalkylene and unsatd. basic acid which is copolymerizable with the vinyl triazine or its deriv. (A), (C) monomers which can produce a formaldehyde addition condensate with the vinyl triazine or its deriv. (A), and (D) a compd. which produces sulfonic groups. In the formula, X1 is H or CH3 , X2 to X5 are independently H, CH2 OH or CH2 SO3 Y, Y is an alkali metal, alkaline earth metal, ammonium, amine or substd. amine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an admixture for a cement or a cement composition, and more particularly, to the addition of a hydraulic cement composition such as a cement paste, mortar, concrete or the like when kneading to improve the workability. The present invention relates to a cement admixture to be improved.

[0002]

2. Description of the Related Art
Various types of organic compounds added to cement, particularly as a cement water reducing agent, are known. Representative examples include salts of highly condensed β-naphthalene sulfonic acid formaldehyde, salts of melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid salts, salts of amino sulfonic acid condensates, and oxycarboxylic acids. . When these compounds are added to a kneaded product composed of cement, water and aggregate, sufficient workability can be obtained even if the amount of water during kneading is reduced. Therefore, there is an advantage that workability is improved, and since the water-cement ratio can be reduced, it is useful for enhancing the strength of a hydraulic cement composition such as cement paste, mortar, and concrete.

[0003] However, in general, cement paste,
Mortar, hydraulic cement composition such as concrete,
With the passage of time after kneading, the fluidity is lost. This phenomenon occurs when the organic compound added as the cement water reducing agent is used, and particularly, β-
This is remarkable when a salt of a highly condensed naphthalenesulfonic acid formaldehyde or the like is used, and depending on the composition of the concrete, a phenomenon in which the slump is reduced to half or less within 30 minutes after kneading is observed. Due to the phenomenon that the slump loss is large, the following problems occur. In other words, the concrete composition may be pumped by pumping concrete, but if the pumping is temporarily interrupted due to a break time or various troubles at that time, the pumping pressure may suddenly increase when resuming, And piping may be blocked. Also, due to reduced fluidity, the compact may not be sufficiently compacted in the mold and a defective portion may be generated.

Therefore, various water reducing agents have been developed in the past in order to suppress slump loss. For example, a substance in which the functional group is dissociated by an alkali in concrete, a so-called sustained-release high-performance water reducing agent (Japanese Patent Publication No. 63-5346) is known. Further, a water-soluble vinyl copolymer (Japanese Patent Publication No. 6-60042) is known, in which a new functional group appears by being hydrolyzed in an alkali and suppresses slump loss. Further, for the purpose of maintaining a slump due to steric hindrance of a molecular chain, a polyalkylene glycol monoester monomer having an unsaturated bond and a (meth) acrylic acid monomer and / or an unsaturated dicarboxylic acid monomer And copolymers thereof (JP-B-59-18338,
Japanese Patent Publication No. 2-7897, Japanese Patent Publication No. 2-7898, Japanese Patent Publication No. 2-7901, Japanese Patent Publication No. 2-8983, Japanese Patent Publication No. 2-11542, Japanese Patent Publication No. 5-110
No. 57, Japanese Patent Publication No. Hei 6-88817) and the like, and water-soluble vinyl copolymers (these are collectively referred to as polycarboxylic acid type). Furthermore, a condensate in which a polyalkylene glycol chain has been introduced into an aromatic compound (JP-A-6-340559) has recently been developed.

[0005] However, while these compounds exhibit excellent flow effects, they have various problems. First,
In the case of sustained-release high-performance water reducing agents that work with alkali in concrete and water-soluble vinyl copolymers that are alkali-hydrolyzed to replenish functional groups and suppress slump loss, carboxyl groups are contained in the compound. Appears over time. This carboxyl group has a large bonding force with calcium ions. Therefore, these compounds trap calcium ions in the cement, and when the amount of addition is large, there is a problem that the setting delay becomes large and the process cannot proceed to the next operation.

Furthermore, a polycarboxylic acid having an oxyalkylene chain in the molecule has high air entrainment, and it is difficult to control the amount of air in concrete. In reality, the amount of air is controlled using an antifoaming agent, but the amount of air fluctuates greatly depending on the kneading conditions in the concrete mixer, the agitator conditions of the mixer truck, and the transport time,
There is a problem that it is difficult to use. Furthermore, (meta)
Since copolymerization is carried out using acrylic acid-based monomers and / or unsaturated dicarboxylic acid-based monomers, these compounds have a carboxyl group in the molecule. However, there is a problem that is increased. That is, the initial strength of the cement mortar or concrete decreases. In addition, when a large slump is used, that is, when soft mortar or concrete is used, material separation may occur, which is a problem.

Further, a condensate in which a polyalkylene glycol chain is introduced into an aromatic compound has a problem that a flow effect similar to that of a polycarboxylic acid having an oxyalkylene chain in a molecule cannot be recognized.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and as a result, it has been found that a compound having a specific molecular structure does not cause remarkable curing delay and has an excellent dispersion effect. The present invention has been found to exhibit a slump holding effect and to have a remarkable resistance to material separation.

That is, the present invention provides an ester of a vinyl triazine or a derivative thereof (A) represented by the following general formula (I), a polyoxyalkylene copolymerizable with the vinyl triazine or a derivative thereof (A), and an unsaturated basic acid. (B) a cement admixture comprising a monomer (C) capable of formaldehyde addition condensation with vinyltriazine or a derivative thereof (A) and a compound (D) capable of forming a sulfone group. General formula (I) X ₁ : H, CH ₃ X _{2 to} X ₅ : each independently H, CH ₂ OH or CH
Y selected from ₂ SO ₃ Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The vinyl triazine represented by the following general formula (I) or its derivative (A) is used in the present invention. General formula (I) X ₁ : H, CH ₃ X _{2 to} X ₅ : each independently H, CH ₂ OH or CH
Y selected from ₂ SO ₃ Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine

The vinyl monomer (A) represented by the general formula (I) is, as shown in JP-B-62-9592, an unsaturated base acid and 2- [β'-2-methylimidazolyl- (1) '] Betaine obtained in high yield from -ethyl-4,6-diamine-s-triazine can be easily obtained by reacting with an alkali in the presence of water.

The vinyl triazine represented by the general formula (I) or its derivative (A) can be used in combination of one or more kinds. For example, 2,4-diamino-6
-Vinyl-s-triazine or its complex salt 2,4-diamino-6-vinyl-1,3,5-triazine isocyanuric acid addition salt.

Vinyl triazine or its derivative (A)
As the ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with a compound represented by the general formula (II): _{X 6, X 7: COOY,} H, CH 3 X 8: H, CH 3 R 1: an alkyl group having 1 to 6 carbon atoms, H, Y: alkali metal, alkaline earth metal, ammonium,
Compounds represented by amines and substituted amines, that is, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, phenoxypolyethylene glycol monoacrylate, phenoxypolyethylene glycol monomethacrylate, and the like can be used.

Vinyl triazine or its derivative (A)
The monomer (C) capable of formaldehyde addition condensation with a compound represented by the general formula (III) Here, X _{9 to} X ₁₄ : independently H, CH ₂ OH
Or CH ₂ SO ₃ Y: Y: alkali metal, alkaline earth metal, ammonium,
Compounds represented by amines and substituted amines, that is, melamine, melamine containing a methylol group, melamine containing a sulfomethyl group, and the like can be used. In the case of sulphomethyl group-containing melamine, salts thereof can also be used. As the salts, inorganic salts, that is, alkali metal salts or alkaline earth metal salts such as potassium, sodium, and magnesium, and organic salts, that is, ammonium salts, monoethanolamine salts, diethanolamine salts, and the like can also be used. The amount is preferably 0.005 to 0.5 mol, more preferably 0.01 to 0.35 mol, per 1 mol of the monomer (C) capable of co-condensing vinyltriazine or its derivative (A) with formaldehyde. Is preferred.

In addition, other than the above, general formula (IV) Here, X ₁₅ : H, CH ₂ OH or CH ₂ SO
₃ Y, a sulfone group or its alkali metal salt, alkaline earth metal salt, ammonium salt, amine, substituted amine Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine R ₂ : a compound represented by H or an alkyl group having 1 to 6 carbon atoms, that is, alkylphenols such as phenol, cresol, pt-butylphenol, pt-amylphenol, or sulfonic acids or A sulfonic acid salt, a methylol group-containing phenol, a sulfomethyl group-containing phenol, or salts thereof can also be used. As the salts,
Similarly to the general formula (II), inorganic salts and organic salts thereof can be used. Among them, phenol, phenol containing a methylol group, phenol containing a sulfomethyl group, or phenolsulfonic acid and salts thereof are preferable in terms of economy and reactivity.

Furthermore, the general formula (V) Here, X _{16 to} X ₁₉ : each independently H, CH ₂ O
Y selected from H or CH ₂ SO ₃ Y: alkali metal, alkaline earth metal, ammonium,
Compounds represented by amines or substituted amines, that is, urea, urea containing a methylol group, and urea containing a sulfomethyl group can also be used. In the case of a sulfomethyl group-containing urea, inorganic salts and organic salts thereof can be used as in the case of the general formula (III).

Further, the compound represented by the general formula (VI) Here, X ₂₀ : H, an alkali metal, an alkaline earth metal, ammonium, an amine, a substituted amine R ₃ : H or an alkyl group having 1 to 6 carbon atoms, that is, aminobenzene sulfone such as sulfanilic acid, metanic acid, or tannic acid Acids or salts thereof can be used. As the salts, inorganic salts and organic salts thereof can be used as in the case of the general formula (IV).
Among them, sulfanilic acid, metanic acid and salts thereof are preferable from the viewpoint of economy and reactivity.

As the compound (D) which produces a sulfone group, known sulfonating agents such as sodium sulfite, sodium bisulfite, sodium pyrosulfite, sulfur dioxide, fuming sulfuric acid and the like can be used. For example, the general formula (III)
Can be carried out by a known method.

That is, the compound can be introduced by adding and condensing melamine with formaldehyde to form methylol melamine, followed by the action of a sulfonating agent and replacement with a hydroxyl group. It is known that 6 mol of formaldehyde is addition-condensed as methylol group to 1 mol of melamine. In the present invention, since it is highly possible that 2 moles of methylol groups are used for cocondensation, sulfomethyl groups can be introduced into the remaining 4 moles of methylol groups at the maximum. Considering the economic aspect and the flow effect of the resulting co-condensate, the amount of sulfomethyl groups introduced is 0.3
４4 mol is preferred, and the introduction of 0.5-2 mol is more preferred. The same applies to the case where a sulfomethyl group is introduced into the phenol of the general formula (IV). The introduction amount is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.5 mol, per mol of phenol. is there. The same applies to the case where a sulfomethyl group is introduced into the urea of the general formula (V), and the amount of introduction is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.5 mol, per mol of urea. .

The formaldehyde used for synthesizing these formaldehyde addition condensates can usually be used at a concentration of 30 to 60% by weight. Further, if necessary, paraform can be used in combination. The amount of formaldehyde used is 1 to 6 times the total number of moles of the monomer (C) capable of formaldehyde addition condensation with vinyltriazine or its derivative (A).
It is preferable to use twice the molar amount. In consideration of economy, ease of the condensation reaction, and the like, it is more preferable to use 1.5 to 4 moles.

The formaldehyde addition condensation reaction is carried out at pH 4 to
The process is carried out in a usual manner in the range of 12, from a weakly acidic region to a basic region. If the pH is less than 4, it is difficult to control the reaction, for example, the condensation reaction may rapidly proceed and gel. In addition, the formaldehyde may be added in advance in the reaction apparatus, or may be reacted by dropping formalin during the reaction.

The composition of the compound constituting the admixture in the present invention is important. That is, vinyl triazine or its derivative (A): an ester of a polyaxylene and an unsaturated basic acid copolymerizable with vinyl triazine or its derivative (A) (B): vinyl triazine or its derivative (A) and formaldehyde addition condensation The molar ratio of possible monomer (C): compound (D) to form a sulfone group: formaldehyde is (0.005-0.5):
(0.005 to 0.5): 1: (0.3 to 4): (1 to
6), and more preferably (0.
01-0.35) :( 0.01-0.4): 1: (0.
5-2): (1.5 to 4) is preferable.

Next, a specific example of a method for producing the cement admixture of the present invention will be described below, but the present invention is not limited thereto. Specific Example 1 Vinyltriazine (A), a part of formaldehyde, and water were charged into a four-necked flask equipped with a stirrer, thermometer, reflux tube, and dropping funnel, and the internal temperature of the reactor was raised to 60 to 90 ° C. Thereafter, the reaction is carried out under a basic condition for 0.5 to 2 hours. Next, an ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with vinyl triazine or its derivative (A) and a polymerization initiator are charged and reacted at 70 to 90 ° C. for 0.5 to 5 hours. Further, the vinyl triazine (A), the monomer (C) capable of formaldehyde addition condensation, and the remaining formaldehyde are added, and the mixture is reacted at 60 to 90 ° C. for 0.5 to 2 hours. Compound (D) that further generates a sulfone group
And reacted at 60 to 90 ° C. for 0.5 to 3 hours. Further, the inside of the system is made weakly acidic, and the reaction proceeds at 50 to 80 ° C. until the viscosity of the solution reaches a predetermined value. When the viscosity of the solution reaches a predetermined value, the reaction is stopped by neutralization. The predetermined viscosity for stopping the reaction varies depending on the nonvolatile content of the solution. When the nonvolatile content is 35% by weight, the value measured with a B-type viscometer is preferably from 7 to 500 cp / 25 ° C.
00 cp / 25 ° C. is more preferred.

Specific Example 2 Vinyl triazine (A) and water are charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a dropping funnel, and the inside of the system is acidified with a mineral acid. Further, an unsaturated hydrocarbon (B) having a polyoxyalkylene group copolymerizable with vinyl triazine or its derivative (A) and a polymerization initiator are charged and reacted at 70 to 90 ° C. for 0.5 to 5 hours. Next, the system is made basic, vinyltriazine (A), a monomer (C) capable of formaldehyde addition condensation and formaldehyde are added, and the mixture is reacted at 60 to 90 ° C. for 0.5 to 2 hours.
Further, a compound (D) which forms a sulfone group is added, and 6
The reaction is carried out at 0 to 90 ° C for 0.5 to 3 hours. Further, the inside of the system is made weakly acidic, and the reaction proceeds at 50 to 80 ° C. until the viscosity of the solution reaches a predetermined value. When the viscosity of the solution reaches a predetermined value, the reaction is stopped by neutralization. The predetermined viscosity at which the reaction is stopped is the same as in Example 1.

The cement admixture of the present invention can be used in combination with other conventionally known water reducing agents, AE water reducing agents, high performance water reducing agents, high performance AE water reducing agents, and fluidizing agents. That is, β-naphthalene sulfonic acid formaldehyde high condensate salt, melamine sulfonic acid formaldehyde condensate salt, amino sulfonic acid condensate salt, lignin sulfonic acid salt, oxycarboxylic acid, polycarboxylic acid type water reducing agent, alkali hydrolysis It can be used in combination with a type water reducing agent, a sustained release high performance water reducing agent, and the like.

As to the method of using the admixture of the present invention, other known cement admixtures such as an air entrainer, an antifoaming agent, a setting accelerator, a setting retarder, a rust inhibitor, a preservative, a waterproofing agent, and a strength accelerator It can be used in combination with an agent or the like. In addition, the method of use is usually mixed in kneading water and added to the cement composition.However, the method of adding the cement composition at once or adding it separately at the time of preparing the cement composition, the method of adding the cement composition after kneading, Any method such as the method of adding may be used. The admixture according to the present invention varies depending on the formulation and the use of the cement composition, but is usually 0.01 to 0.01 in terms of solid content relative to cement.
It is used in a proportion of 5.0% by weight, preferably 0.05 to 3.0% by weight. If the amount used is less than 0.01% by weight,
This is not preferred because the dispersion fluidity tends to decrease and the effect of preventing slump loss tends to decrease. On the other hand, if the content exceeds 5.0% by weight, it tends to cause material separation, making it difficult to obtain a homogeneous cured product, and is disadvantageous economically, which is not preferable.

The cement admixture according to the present invention can be applied to concrete and mortar prepared using various portland cements, fly ash cements, blast furnace cements, silica cements, various types of mixed cements and the like. Furthermore, the present invention can be applied to concrete containing silica fume, blast furnace slag, limestone fine powder and the like.

It is not clear why the cement admixture of the present invention exhibits an excellent flow effect, a slump loss suppressing effect and a material separation resistance without showing a setting delay, but it is presumed as follows. That is, since the admixture of the present invention has a sulfone group in the molecule similarly to the conventional high-performance water reducing agent,
The electric repulsion enhances the dispersibility of the cement particles. Moreover, when the admixture of the present invention is adsorbed on the cement particles, it is considered that the polyoxyalkylene group contained in the molecule extends outside the cement particles. A hydration layer is formed around the polyoxyalkylene group extending outward, and it is thought that the steric hindrance effect accompanying the hydration layer maintains the dispersibility of the cement particles for a long time and suppresses slump loss. Furthermore, as in the conventional sustained-release high-performance water reducing agent, polycarboxylic acid-based water reducing agent, and alkali hydrolysis-type water reducing agent, C is contained in the molecule.
Since it does not have an a ion and a carboxyl group having a high chelating ability, it is not expected to exhibit a setting retardation. therefore,
The admixture of the present invention has excellent dispersion performance, slump loss suppressing effect, and material separation resistance.

The admixture of the present invention will be described in more detail in the following Examples, but the present invention is not limited thereto. In addition, all percentages or parts described below as units of numerical values are% by weight or parts by weight unless otherwise specified. The vinyltriazine (A) used in the examples is composed of an unsaturated basic acid and 2- [β'-2-methylimidazolyl- (1 ')]-ethyl as disclosed in JP-B-62-9592. -4,6-diamine-s-
2-vinyl-4,6-diamino-s-triazine produced by reacting the corresponding betaine obtained from a triazine with an alkali in the presence of water was used.

[0030]

The present invention will be described below in more detail with reference to production examples and examples. In addition,% and part represent weight% and part by weight unless otherwise specified. Production Example 1 2-vinyl-4,6-diamino-s-triazine 0.4
Mol (54.9 parts), 0.4 mol (4.4 parts) of 37% formalin and 472.0 parts of water were charged into a four-necked flask equipped with a stirrer, thermometer, reflux tube and dropping funnel, and reacted. After the temperature in the vessel was raised to 70 ° C., the reaction was carried out for 1 hour under basic conditions. Next, 0.3 mol (87.9 parts) of NK ester M40G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and a polymerization initiator were charged and reacted at 90 ° C. for 2 hours to give melamine 0.53.
Mol (66.8 parts), phenol 0.12 mol (11.
3 parts), 0.2 mol (12.0 parts) of urea, 0.15 mol (26.0 parts) of sulfanilic acid and 2.6 mol (210.8 parts) of 37% formaldehyde. After 0.5 hours of reaction, 0.54% of sodium bisulfite was added.
Mole (56.2 parts) was added and reacted at 80 ° C. for 1.5 hours. Next, 126.0 parts of water was added and the mixture was cooled to 60 ° C. The pH was adjusted to 6.0 with 40% sulfuric acid, the temperature was raised to 65 ° C, and the reaction was performed. When the viscosity of the solution reached 24 cp / 25 ° C, the reaction was stopped by neutralizing with a 25% aqueous sodium hydroxide solution. Was. The obtained product was designated as copolymer 1.

Production Example 2 In a four-necked flask equipped with a stirrer, thermometer, reflux tube and dropping funnel, 0.1 mol (13.7 parts) of 2-vinyl-4,6-diamino-s-triazine, water After charging 625.0 parts by weight, the inside of the system was acidified with 40% sulfuric acid. Further, NK ester M230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.1
Mole (106.8 parts) and a polymerization initiator, and charged at 90 ° C.
For 2 hours, and the system is purged with 25% sodium hydroxide.
H was 11.5, and 1.0 mole of melamine (126.1
2.9 mol (235.1 parts) of 37% formalin, and reacted at 75 ° C. for 1 hour. Further, 0.8 mol (83.3 parts) of sodium bisulfite was added and the mixture was added at 85 ° C for 2 hours.
After reacting for an hour, cool to 60 ° C. and p
After adjusting to H 6.0, the viscosity of the solution was 26 cp / 25 ° C.
Was reached, the reaction was stopped by neutralizing with a 25% aqueous sodium hydroxide solution. The obtained product was designated as copolymer 2.

Production Examples 3 and 4 The same procedures as in Production Example 1 were carried out except that the compounds shown in Table 1 were used. As a result, copolymers 3 and 4 were obtained.

Production Examples 5 to 6 The same procedures as in Production Example 2 were carried out except that the compounds shown in Table 1 were used. As a result, copolymers 5 to 6 were obtained.

Production Example 7 The same procedure as in Production Example 1 was carried out except that the vinyltriazine represented by the general formula (I) or its derivative (A) was not used. As a result, a copolymer 7 was obtained as shown in Table 1.

Production Example 8 The same procedure as in Production Example 1 was carried out except that the ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with vinyltriazine or its derivative (A) was not used. As a result, a copolymer 8 was obtained as shown in Table 1.

Production Example 9 Production was carried out in the same manner as in Production Example 1 except that a monomer (C) capable of formaldehyde addition condensation with vinyltriazine or its derivative (A) was not used. As a result, a copolymer 9 was obtained as shown in Table 1.

Production Example 10 The same procedure as in Production Example 1 was carried out except that the compound (D) which produces a sulfone group was not used. As a result, a copolymer 10 was obtained as shown in Table 1.

[0038]

[Table 1]

Example 1 Using a 50 liter forced biaxial concrete mixer, based on the concrete test formulation shown in Table 2,
Cement, coarse aggregate, copolymer 1 obtained in Production Example 1 and water were added so that the amount of kneading was 1 liter,
The mixture was kneaded for 90 seconds, the coarse aggregate was added, and kneaded for 3 minutes. A highly fluid concrete having a slump of 18 cm and an air volume of 3% was prepared. To achieve the target air volume, use the air entrainer Vinsol manufactured by Yamamune Chemical Co., Ltd. if the entrained air volume is insufficient, and use Hokukon Sangyo Co., Ltd. as an antifoaming agent if the air volume is too high. It was adjusted by using Delkrite 850 manufactured by KK. After kneading, slump and slump flow with time were measured every 30 minutes until 90 minutes later. In addition, the compressive strength was measured in 1 day, 7 days, and 28 days by preparing a cylindrical specimen having a diameter of 10 cm and a height of 20 cm. Regarding the material separation resistance, the degree of movement of the aggregate during slump flow measurement was visually observed, and relative evaluations of ◎, 、, Δ, and × were made. In addition, the method of measuring the slump, the amount of air, the setting time and the compressive strength, and the method of preparing the specimen for compressive strength were all based on Japanese Industrial Standards (JIS-A6204). Table 3 shows the results.

[0040]

[Table 2] W / C: water / cement (% by weight) s / a: fine aggregate / (fine aggregate + coarse aggregate) (volume%) C: cement S: fine aggregate G: coarse aggregate Concrete kneading material cement : Three kinds of ordinary Portland cement (Mitsubishi Materials Corporation, Chichibu Onoda Corporation, Tokuyama Corporation)
Specific gravity = 3.16 Fine aggregate: Weathered granite sand from Irino, Kawachi-cho, Kamo-gun, Hiroshima Prefecture
Specific gravity = 2.57 Coarse aggregate: Hard sandstone crushed stone from ishiishi-shaped wall stone in Shimonoseki-shi, Yamaguchi Prefecture Crushed stone 5: Crushed stone 6 = 1: 1: 1 Specific gravity = 2.69

Examples 2 to 6 The same operation as in Example 1 was performed except that copolymers 2 to 6 were used. Table 3 shows the results.

Comparative Examples 1 to 4 The same operation as in Example 1 was performed except that copolymers 7 to 10 were used. Table 3 shows the results.

Comparative Examples 5 to 9 As a comparative water reducing agent, a commercially available high-performance water reducing agent, Melflow 40 (Mitsui Toatsu Chemical Co., Ltd .: melamine),
Mighty 150 (Kao Corporation: naphthalene type), Palic FP200U (Fujisawa Pharmaceutical Co., Ltd .: aminosulfonic acid type), sustained release type Mighty 2000WH which is a high performance AE water reducing agent (Kao Corporation: naphthalene type + The same operation as in Example 1 was performed using Tupole HP-8 (Takemoto Oil & Fats Co., Ltd .: polycarboxylic acid system). Table 3 shows the results.

[0044]

[Table 3]

[0045]

According to the present invention, it has been found that a compound having a specific molecular structure exhibits an excellent dispersing effect and a slump holding effect without remarkable curing delay, and furthermore has a remarkable material separation resistance. The cement admixture obtained by the present invention has the characteristics of exhibiting a high flow effect at a low addition amount, having a high flow retention rate, and having excellent one-day strength, as compared with existing cement water reducing agents. That is, it has high initial fluidity and excellent slump holding properties without causing hardening delay for cement compositions such as mortar and concrete. Furthermore, it has excellent material separation resistance. Therefore, when the cement admixture obtained by the present invention is used for civil engineering and construction-related works, workability can be significantly improved.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 29, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 8

[Correction method] Change

[Correction contents]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

The ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with vinyl triazine or its derivative (A) is represented by the general formula (II): _{Independently, X 6, X 7: COOY} , H, CH 3 X 8: H, CH 3 R 1: an alkyl group having 1 to 6 carbon atoms, H, Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine n: a compound represented by an integer of 2 to 300 , that is, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, phenoxypolyethylene glycol monoacrylate, phenoxypolyethylene glycol monomethacrylate, or the like can be used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Deleted

[Correction contents]

Vinyl triazine or its derivative (A)
The monomer (C) capable of formaldehyde addition condensation with a compound represented by the general formula (III) Here, X _{9 to} X ₁₄ : independently H, CH ₂ OH
Or CH ₂ SO ₃ Y: Y: alkali metal, alkaline earth metal, ammonium,
Compounds represented by amines and substituted amines, that is, melamine, melamine containing a methylol group, melamine containing a sulfomethyl group, and the like can be used. In the case of sulphomethyl group-containing melamine, salts thereof can also be used. As the salts, inorganic salts, that is, alkali metal salts or alkaline earth metal salts such as potassium, sodium, and magnesium, and organic salts, that is, ammonium salts, monoethanolamine salts, diethanolamine salts, and the like can also be used.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

In addition, other than the above, general formula (IV) Here, X ₁₅ : H, CH ₂ OH or CH ₂ SO
₃ Y, a sulfone group or its alkali metal salt, alkaline earth metal salt, ammonium salt, amine, substituted amine Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine R ₂ : a compound represented by H or an alkyl group having 1 to 6 carbon atoms, that is, alkylphenols such as phenol, cresol, pt-butylphenol, pt-amylphenol, or sulfonic acids or A sulfonic acid salt, a methylol group-containing phenol, a sulfomethyl group-containing phenol, or salts thereof can also be used. As the salts,
Similarly to the general formula (III) , inorganic salts and organic salts thereof can be used. Among them, phenol, phenol containing a methylol group, phenol containing a sulfomethyl group, or phenolsulfonic acid and salts thereof are preferable in terms of economy and reactivity.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

Further, the compound represented by the general formula (VI) Here, X ₂₀ : H, an alkali metal, an alkaline earth metal, ammonium, an amine, a substituted amine R ₃ : H or an alkyl group having 1 to 6 carbon atoms, that is, aminobenzene sulfone such as sulfanilic acid, metanic acid, or tannic acid Acids or salts thereof can be used. As the salt, a compound represented by the general formula (III)
Similarly to the above, inorganic salts and organic salts thereof can be used. Among them, sulfanilic acid, metanic acid and salts thereof are preferable from the viewpoint of economy and reactivity.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

The composition of the compound constituting the admixture in the present invention is important. That is, vinyl triazine or a derivative thereof (A): vinyltriazine or ester derivative thereof (A) copolymerizable with polio Kishiarukiren and unsaturated basic acid (B): vinyl triazine or a derivative thereof (A) with formaldehyde added The molar ratio of the condensable monomer (C): the compound (D) that forms a sulfone group: formaldehyde is (0.005 to 0.5):
(0.005 to 0.5): 1: (0.3 to 4): (1 to
6), and more preferably (0.
01-0.35) :( 0.01-0.4): 1: (0.
5-2): (1.5 to 4) is preferable.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

Example 1 Using a 50 liter forced biaxial concrete mixer, based on the concrete test formulation shown in Table 2,
Cement, coarse aggregate, copolymer 1 obtained in Production Example 1 and water were added so that the amount of kneading was 1 liter,
The mixture was kneaded for 90 seconds, the coarse aggregate was added, and kneaded for 3 minutes. Slump flow 60 ± 2 cm, air volume 3 ±
A 1 % high fluidity concrete was prepared. To achieve the target air volume, use the air entrainer Vinsol manufactured by Yamamune Chemical Co., Ltd. if the entrained air volume is insufficient, and use Hokukon Sangyo Co., Ltd. as an antifoaming agent if the air volume is too high. It was adjusted by using Delkrite 850 manufactured by KK. After kneading, slump and slump flow with time were measured every 30 minutes until 90 minutes later. The compressive strength is φ10cm x height 20cm
Was prepared, and the measurement was performed in 1 day, 7 days, and 28 days. Regarding the material separation resistance, the degree of movement of the aggregate was visually observed during slump flow measurement, and ◎, ○,
The relative evaluation of Δ and × was performed. The methods for measuring the slump, the amount of air, the setting time and the compressive strength, and the method for preparing the specimen for compressive strength are all Japanese Industrial Standards (JIS-A620).
Performed according to 4). Table 3 shows the results.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshihiko Tomita 7-1-1, Hikoshimasako-cho, Shimonoseki-shi, Yamaguchi Pref.

Claims (8)

[Claims] 1. An ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with vinyl triazine or its derivative (A) represented by the following general formula (I) or vinyl triazine or its derivative (A): A cement admixture comprising a monomer (C) capable of formaldehyde addition condensation with vinyltriazine or its derivative (A) and a compound (D) capable of forming a sulfone group. General formula (I) X ₁ : H, CH ₃ X _{2 to} X ₅ : each independently H, CH ₂ OH or CH
Y selected from ₂ SO ₃ Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine 2. The cement admixture according to claim 1, wherein the ester (B) of a polyoxyalkylene and an unsaturated basic acid copolymerizable with vinyltriazine or its derivative (A) is represented by the following general formula (II). . General formula (II) _{X 6, X 7: COOY,} H, CH 3 X 8: H, CH 3 R 1: an alkyl group having 1 to 6 carbon atoms, H, Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine 3. A monomer (C) capable of formaldehyde addition condensation with vinyltriazine or its derivative (A).
Is one or more compounds selected from the group consisting of melamine or a derivative thereof, phenol or a derivative thereof, urea or a derivative thereof, aminobenzenesulfonic acid or a derivative thereof, and alkylaminobenzenesulfonic acid or a derivative thereof. The cement admixture according to 1 above. 4. A compound (D) which forms a sulfone group
The cement admixture according to claim 1, wherein the admixture comprises one or more compounds selected from the group consisting of sodium sulfite, sodium bisulfite, sodium pyrosulfite, fuming sulfuric acid, and sulfur dioxide. 5. The cement admixture according to claim 3, wherein the melamine or a derivative thereof is represented by the following general formula (III). General formula (III) Here, X _{9 to} X ₁₄ : independently H, CH ₂ OH
Or Y selected from CH ₂ SO ₃ Y: an alkali metal, an alkaline earth metal, ammonium,
Amine, substituted amine 6. The cement admixture according to claim 3, wherein the phenol or a derivative thereof is represented by the following general formula (IV). General formula (IV) Here, X ₁₅ : H, CH ₂ OH or CH ₂ SO
₃ Y, a sulfone group or its alkali metal salt, alkaline earth metal salt, ammonium salt, amine, substituted amine Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine R ₂ : H or alkyl group having 1 to 6 carbon atoms 7. The cement admixture according to claim 3, wherein the urea or a derivative thereof is represented by the following general formula (V). General formula (V) Here, X _{16 to} X ₁₉ : each independently H, CH ₂ O
Y selected from H or CH ₂ SO ₃ Y: alkali metal, alkaline earth metal, ammonium,
Amine, substituted amine 8. The cement admixture according to claim 3, wherein the aminobenzenesulfonic acid or a derivative thereof or the alkylaminobenzenesulfonic acid or a derivative thereof is represented by the following general formula (VI). General formula (VI) Here, X ₂₀ : H, alkali metal, alkaline earth metal, ammonium, amine, substituted amine R ₃ : H or an alkyl group having 1 to 6 carbon atoms