JP2008230865A - Additive for hydraulic material and hydraulic material composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for a hydraulic material effectively reducing the autogenous shrinkage and drying shrinkage without having large effect on the physical property, particularly the dispersiblity and hardening property of the hydraulic material. <P>SOLUTION: The additive for the hydraulic material contains a polyamine compound having a polyamine structure as a main chain and a group having an essential component originated from glycidyl ether having a 1-30C hydrocarbon as a side chain (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an additive for hydraulic material and a hydraulic material composition containing the additive. In particular, the present invention relates to an additive for a hydraulic material that reduces self and dry shrinkage of a hydraulic material, particularly a concrete member, and a hydraulic material composition containing the additive.

  Concrete admixtures are widely used in cement compositions such as cement paste, mortar, and concrete because they can provide excellent strength and durability. It is impossible. In such a cement composition, after it hardens, the unreacted water remaining in the interior is dissipated due to the outside air temperature and humidity conditions, etc. There was a problem that occurred.

  In addition, for the purpose of improving durability, a high-strength hydraulic material having a reduced water binder ratio (W / B: mass ratio of water and binder) has been widely used. However, in these high-strength hydraulic materials, as W / B becomes lower, curing (hydration) unevenness tends to occur inside the material, and unreacted water remaining in the cured portion is insufficiently cured. When moving to the part, a tensile force is generated between the capillary surface formed by curing and water, and self-shrinkage, which is considered to be caused by this, proceeds in the cured product during curing or in the initial stage immediately after curing. There was a problem that cracks occurred.

  Furthermore, in recent years, materials such as blast furnace slag fine powder have been used as a part of hydraulic materials from the viewpoint of improving durability and environmental load. However, these hydraulic materials such as blast furnace slag It has been pointed out that when powder is used, cracking is likely to occur because the shrinkage is larger than when conventional Portland cement is used. These cracks not only detract from the aesthetics of the structure, but over the long term, deterioration factors such as air (especially carbon dioxide) and rainwater (especially acid and chloride ions) infiltrate through the cracks. It has been pointed out that it induces many complex deteriorations, such as neutralization and, in turn, promoting corrosion of reinforcing bars. In recent years, the early deterioration of these concrete structures has become a social problem, and the demand for highly durable structures that suppress cracking and has increased. Furthermore, the importance of shrinkage reducing agents for hydraulic materials that suppress the progress of shrinkage caused by hydraulic materials used other than cement, such as blast furnace slag fine powder and fly ash, is recognized, and There is a lot of innovation.

  Against this background, many research reports on shrinkage reduction have been made. As a method for reducing shrinkage and thus suppressing cracking, there are a method for reducing the unit water content of a concrete composition using a water reducing agent, and an expansion material. And a method using a shrinkage reducing agent. Among these, the method of reducing the unit water amount using a water reducing agent is widely used as the simplest method. Currently, naphthalene-based, aminosulfonic acid-based, polycarboxylic acid-based, and the like are commercially available as such water reducing agents. In the polycarboxylic acid-based high-performance AE water reducing agent having the most excellent characteristics, various water-soluble agents are used. Vinyl copolymers have been proposed (see, for example, Patent Documents 1 to 5). However, in these water reducing agents, the shrinkage reduction performance is not sufficient, and a method in which an expansion material or a shrinkage reducing agent is further used as required is employed. At this time, various compounds are used as the shrinkage reducing agent used together (for example, see Patent Documents 6 to 9). Among the above publications, Patent Document 6 discloses a cement shrinkage prevention agent containing an addition polymer of propylene oxide and ethylene oxide. Patent Document 8 discloses a shrinkage reducing agent containing an alkylene oxide adduct of a diphenylmethane derivative.

  However, the use of such a shrinkage reducing agent and shrinkage reducing agent is necessary because the amount of both the expansion agent and shrinkage reducing agent must be increased in the concrete composition, and the product price of the shrinkage reducing agent is high. This leads to a significant increase in unit price per concrete unit capacity. Such a problem contributes to the fact that shrinkage reducing agents are not popular in the market.

  As a measure for solving these problems, for example, Patent Document 10 discloses a polymer obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid to an alkoxy polyalkylene glycol. However, in the polymer disclosed in Patent Document 10, the dispersibility and the shrinkage reduction cannot be satisfied at the same time, and the above problem cannot be solved sufficiently.

Patent Document 11 discloses a polyamine compound containing a hydrocarbon group having 4 to 30 carbon atoms as an essential component.
JP-A-8-53522 JP-A-8-290948 JP-A-8-290955 Japanese Patent Laid-Open No. 9-2855 JP-A-10-81549 JP 59-21577 A JP 59-3430 A JP 62-61450 A Japanese Patent No. 2825855 JP 2001-247346 A International Publication No. 2005/087684 Pamphlet

  However, the compound disclosed in Patent Document 11 is improved in shrinkage reduction as compared with the shrinkage reducing agents described in Patent Documents 1 to 10, but has dispersibility. When used in large quantities, the separation of aggregates (material separation) of the hydraulic material composition occurs, so there is a limit to the shrinkage reduction performance that can be achieved, and further, the physical properties of hydraulic materials such as causing significant delay in curing. There was a drawback of affecting the

  Thus, although there is a strong demand for an additive that can effectively reduce self and drying shrinkage without greatly affecting the general physical properties of the hydraulic material, such an additive has not been obtained.

  Accordingly, the present invention has been made in view of the above circumstances, and is hydraulic capable of effectively reducing self and drying shrinkage without significantly affecting the physical properties of the hydraulic material, in particular, dispersibility and curing characteristics. It aims at providing the additive for materials.

  Another object of the present invention is to provide an additive composition for a hydraulic material that can effectively reduce self and drying shrinkage without significantly affecting the physical properties of the hydraulic material, particularly dispersibility and curing properties. That is.

  Yet another object of the present invention is to provide a hydraulic material composition that effectively reduces self and drying shrinkage.

  In order to achieve the above-mentioned objects, the present inventors have conducted extensive studies on various compounds. As a result, glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms is used as a hydrophobic group in the polyamine compound. Since the compound obtained by introducing into the chain can exhibit excellent self and drying shrinkage reduction properties, it was found that this compound is useful as an additive for hydraulic materials. In addition to the above knowledge, in addition to glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms, it is obtained by further introducing side chains derived from oxyalkylene, carboxylic acid / salt, hydroxyalkyl ester, etc. into the polyamine compound. Since the obtained compound has less influence on the physical properties of the hydraulic material and can exhibit self and drying shrinkage reduction properties, it has been found that this compound is also useful as an additive for hydraulic materials. Based on the above findings, the present invention has been completed.

  That is, the above purpose is hydraulic having a polyamine compound having a polyamine structure as a main chain and a side chain (1) having a glycidyl ether-derived group having a hydrocarbon group having 1 to 30 carbon atoms as an essential component. Achieved by material additives.

In the present invention, the polyamine compound has, as the side chain (2), an oxyalkylene group having 2 to 4 carbon atoms; —COOZ (where Z is a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, an organic amine group) or ^- represents ^{_{(R 2 O) n -R 3}} , this time ^{R 2} O represents one kind or a mixture of two or more oxyalkylene group having 2 to 18 carbon atoms, n is an oxyalkylene group ( R ² O) represents the average number of moles added, is a number from 1 to 500, R ³ represents a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms); and —SO ₃ W (W is And at least one group selected from the group consisting of a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, and an organic amine group.

  The above object is also achieved by a shrinkage reducing composition comprising at least one hydraulic material additive and dispersant of the present invention.

The additive for hydraulic material of the present invention has a polyamine structure as a main chain, and a polyamine having, as an essential component, a group derived from a glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms as a side chain (1). It is characterized by a compound. The polyamine compound according to the present invention can effectively suppress self and drying shrinkage of the cement material. For this reason, by using the additive for hydraulic materials of the present invention, self and drying shrinkage can be effectively reduced, so that high durability of the concrete can be achieved. In addition, the polyamine compound according to the present invention includes an oxyalkylene group having 2 to 4 carbon atoms; —COOZ (where Z is a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, an organic amine group, or — (R ² O ) _N -R ³ , wherein R ² O represents one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms, and n is an average of oxyalkylene groups (R ² O) Represents the number of added moles, is a number from 1 to 500, R ³ represents a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms; and —SO ₃ W (W is a hydrogen atom, monovalent) By further introducing at least one group selected from the group consisting of metals, divalent metals, ammonium groups, and organic amine groups), the self and drying shrinkage reduction effects can be further improved, and the concrete resistance It is possible to improve the resistance.

  Therefore, the hydraulic material additive of the present invention is applied to hydraulic materials such as cement paste, mortar, concrete, etc., and exhibits an excellent crack prevention effect, thereby improving the strength and durability of the cured product. It is highly versatile and can improve the safety of civil engineering and building structures, and can reduce repair costs.

  Hereinafter, embodiments of the present invention will be described in detail.

  The first of the present invention is a water having a polyamine compound having a polyamine structure as a main chain and a side chain (1) having a glycidyl ether-derived group having a hydrocarbon group having 1 to 30 carbon atoms as an essential component. An additive for hard materials is provided. The side chain-containing polyamine compound according to the present invention exhibits excellent self and drying shrinkage reduction properties. In this specification, a polyamine compound after a group derived from a glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms is referred to as a “side chain (1) -containing polyamine compound”, and the polyamine before introduction The compound is referred to as “polyamine compound (I)”. The clear mechanism by which the side chain-containing polyamine compound according to the present invention can suppress self- and dry shrinkage is unknown, but is considered as follows. That is, unreacted water (free water) moves inside the hardened body as the hardening process by hydration of concrete and drying of the hardened concrete after hardening. At that time, it is said that shrinkage occurs because a tensile force is generated by the surface tension of water between the surface of the cured body and water. In particular, when W / B is higher than 40%, shrinkage due to drying, so-called drying shrinkage, and when W / B is lower than 40%, self-shrinkage that occurs during the hydration process becomes a major factor of each shrinkage. It is said. For this reason, the purpose of the self and dry shrinkage reducing agent is to reduce the tensile force between the surface of the cured body and the water generated by the movement of water by lowering the surface tension of water. In the chain (1) -containing polyamine compound, a group derived from a glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms, which is an essential component, acts as a hydrophobic group, and this hydrophobic group portion is the side chain. (1) When the contained polyamine compound is dissolved in water, it is considered that the effect of lowering the surface tension of water is exhibited, thereby suppressing self and drying shrinkage. It should be understood that the present invention is not limited by the above consideration.

  In the present invention, the main chain of the polyamine compound is not particularly limited as long as it has a polyamine structure, and examples thereof include polyalkyleneimine, polyamide polyamine, polyurea polyamine, polyamide polyester polyamine, polyallylamine and polyallylpolyamine. . Among these, polyalkyleneimine and polyallylamine are preferable, and polyalkyleneimine is more preferable. That is, the polyamine compound according to the present invention includes polyamine compounds having a polyamine structure such as polyalkyleneimine, polyamide polyamine, polyurea polyamine, polyamide polyester polyamine, polyallylamine and polyallyl polyamine as the main chain, and preferably polyamine compounds as the main chain. A polyamine compound having an alkyleneimine or polyallylamine, more preferably a polyamine compound having a polyalkyleneimine as the main chain.

In addition to the side chain (1), the side chain (1) -containing polyamine compound according to the present invention includes an oxyalkylene group having 2 to 4 carbon atoms; -COOZ (provided that Z Represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, an organic amine group, or — (R ² O) _n —R ³ , where R ² O is an oxyalkylene group having 2 to 18 carbon atoms. represents one or a mixture of two or more, n is a mean addition mol number of the oxyalkylene group ^(R 2 O), the number of 1 to 500, ^{R 3} is 1 to hydrogen or carbon atoms And —SO ₃ W (wherein W represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group), and at least one group selected from the group consisting of —SO ₃ W More preferably as side chain (2) There (herein, the side chains (1) and a compound having a (2), also simply referred to as "side chain (1, 2) containing polyamine compound"). The side chain (1,2) -containing polyamine compound according to the present invention can effectively reduce self and drying shrinkage. Although the clear mechanism in which the side chain (1,2) -containing polyamine compound according to the present invention exhibits excellent self and drying shrinkage reduction properties is unknown, it can be considered as follows. That is, similarly to the above, by introducing a hydrophobic group called a glycidyl ether-derived group having a hydrocarbon group having 1 to 30 carbon atoms in the polyamine compound as a side chain, the interfacial tension of the cured body surface and water is lowered. It is considered that the tensile stress between water and the surface of the cured body, which occurs with the movement of water inside the cured body, which is the cause of self and dry shrinkage, can be reduced, and as a result, self and dry shrinkage can be suppressed. . Moreover, by introducing a group derived from oxyalkylene, carboxylic acid or a salt thereof, and sulfonic acid or a salt thereof as a side chain (2), the side chain (1,2) -containing polyamine compound can be adsorbed on the cement surface. When the side chain (1,2) -containing polyamine compound is adsorbed on the cement surface, the cement surface is hydrophobized, and the effect of reducing the tensile force between the hardened body surface and water is exhibited. It is considered that the drying shrinkage reduction property is further increased. It should be understood that the present invention is not limited by the above consideration.

  Further, the side chain (1) -containing polyamine compound according to the present invention is, as will be described in detail below, in addition to the side chain (1) or the side chains (1) and (2), -COOZ ′ (where Z It is preferable that 'represents a hydrocarbon group having 1 to 3 carbon atoms) as a side chain (3) (in this specification, such a compound is simply referred to as "side chain (1, 3)". Also referred to as "containing polyamine compound"). At this time, the side chain (3) is particularly preferably introduced at a ratio of 2.4 or less per one side chain (1). The side chain (1,3) -containing polyamine compound according to the present invention in which the specific amount of the side chain (3) is introduced can effectively reduce self- and dry shrinkage. The clear mechanism by which the side chain (1,3) -containing polyamine compound according to the present invention exhibits excellent self and drying shrinkage reduction properties is unknown, but is considered as follows. That is, by the introduction of the side chain (3), adsorption of the polyamine compound to the cement particle surface occurs, and the tensile force generated between the cured body surface and water is reduced by hydrophobizing the cured body surface, It is considered that this can further increase the self and drying shrinkage reduction effects. It should be understood that the present invention is not limited by the above consideration.

  For this reason, the additive for hydraulic material of the present invention is usually used for various portland cements such as early strong, moderately hot, low heat, sulfate resistant, high belite containing cement, alumina cement, blast furnace cement, fly ash cement, various It is preferably used for hydraulic cements such as mixed cements or hydraulic materials other than cements such as gypsum for the purpose of effectively reducing self and drying shrinkage.

  The polyamine compound (I) according to the present invention is a compound having a primary and / or secondary amino group in its molecule. The polyamine compound (I) is not particularly limited as long as it has a primary and / or secondary amino group in its molecule. For example, amines having such a group or derivatives thereof There is. Among these, examples of the amines include polyalkylenimines obtained by polymerization or copolymerization of alkyleneimines (eg, ethyleneimine, azetidine, pyrrolidine, piperidine, etc.) such as polyethyleneimine obtained by polymerization of ethyleneimine; By condensation of polyalkyleneimines and / or (poly) alkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polybasic acids such as sulfuric acid, phosphoric acid, adipic acid, etc. Polyamide polyamine obtained; polyurea polyamine obtained by reaction of polyalkyleneimine and / or alkyleneimine with urea; acid anhydride such as alkyleneimine and phthalic anhydride Polyester polyesters obtained by copolymerization with polyarylamine; and polydiallylamine-dioxide obtained by copolymerization of polyallylamine, diallylamine and / or its hydrochloride and sulfur dioxide obtained by polymerization of allylamine, diallylamine and / or its hydrochloride Examples thereof include a sulfur copolymer, diallylamine and / or a diallylamine-maleic acid copolymer obtained by copolymerization of a hydrochloride thereof and maleic acid. Examples of polyamine derivatives include the above polyamines, alkylene oxides such as ethylene oxide and propylene oxide, (meth) acrylic acid esters such as butyl acrylate and methyl methacrylate, and α, β-unsaturated amide compounds such as acrylamide. And the like. Of these, polyalkyleneimine is preferable, that is, the main chain is preferably polyalkyleneimine. In addition, although polyamine compound (I) by this invention may be manufactured by superposition | polymerization or an addition reaction as mentioned above, you may use a commercial item. Commercially available products include Epomin (registered trademark) (polyethyleneimine) SP-003, SP-006, SP-012, SP-018, SP-200, SP-110, P-1000 (Nippon Shokubai Co., Ltd.), polyallylamine (Registered trademark) PAA-03, PAA-05, PAA-08, PAA-15, PAA-15B, PAA-10C, PAA-25 (Nittobo Co., Ltd.), diallylamine / maleic acid copolymer PAS-410, PAS -410S (Nittobo Co., Ltd.). Among these, polyalkyleneimine, polyamide polyamine, polyallylamine, polyethyleneimine, a condensate of ethylenediamine and adipic acid, a condensate of triethylenetetramine and adipic acid, and a diallylamine-maleic acid copolymer are preferable, polyalkyleneimine, Polyamide polyamine and polyallylamine are more preferable, polyalkyleneimine and polyamide polyamine are particularly preferable, and polyalkyleneimine is most preferable. The polyamine compound (I) according to the present invention may be used alone or in the form of a mixture of two or more.

  In the present invention, the molecular weight of the polyamine compound (I) is not particularly limited, but is preferably 300 to 500,000. At this time, if the molecular weight is less than 300, the amount of the side chain (1) added is small, and sufficient self and dry shrinkage reduction properties may not be obtained. Conversely, when the molecular weight exceeds 500,000, the polyamine compound (I) becomes too large, and the side chain (1) and, if necessary, the side chain (2) / (3) are introduced into the polyamine compound (I). The molecular weight of the polyamine compound after the treatment is excessively large, and the hydration reaction after adsorption on the cement particle surface is inhibited, so that there is a possibility that the setting time is significantly delayed and the strength is lowered. The molecular weight of the polyamine compound (I) is more preferably 300 to 300,000, further preferably 300 to 100,000, and most preferably 600 to 50, in view of self and drying shrinkage reduction and the influence on the setting time. 000. In the present specification, the molecular weight means a number average molecular weight (Mn) measured by gel permeation chromatography (GPC).

  Moreover, in this invention, the side chain (1) containing polyamine compound introduce | transduced the group derived from the glycidyl ether which has a C1-C30 hydrocarbon group as a side chain (1) in polyamine compound (I). It is. In the present invention, the side chain (1) -containing polyamine compound may be a single side chain (1) introduced into the polyamine compound (I), or two or more types of side chains (1). It may be coexisted in the polyamine compound (I). At this time, the method for introducing the side chain (I) is not particularly limited, but generally, the polyamine compound (I) is glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms (in the present specification, (Referred to as “glycidyl ether (II)”). By reacting glycidyl ether (II) with polyamine compound (I), glycidyl ether (II) is introduced into the side chain (1) of polyamine compound (I) as a hydrophobic group. When dissolved in water by the introduction of this hydrophobic group, the effect of lowering the surface tension of water is manifested, and during the curing reaction and drying, the surface of the cured body generated by the movement of water inside the cured body and water The tensile force is reduced, and as a result, the effect of effectively suppressing self and drying shrinkage is imparted to the side chain (1) -containing polyamine compound.

  Specific examples of such glycidyl ether (II) include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, sec-butyl glycidyl ether, tert- Alkyl glycidyl ethers of lower and higher alcohols such as butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether; octylphenyl glycidyl ether, nonylphenyl glycidyl ether, laurylphenyl glycidyl Alkyl compounds such as ether stearyl phenyl glycidyl ether Alkyl glycidyl ethers; octylcyclopentyl glycidyl ether, octyl cyclohexyl glycidyl ether, nonyl cyclopentyl glycidyl ether, nonyl cyclohexyl glycidyl ether, lauryl cyclopentyl glycidyl ether, lauryl cyclohexyl glycidyl ether, stearyl cyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether, etc. And glycidyl ethers of alkyl benzyl alcohol such as octyl benzyl glycidyl ether, nonyl benzyl glycidyl ether, lauryl benzyl glycidyl ether and stearyl benzyl glycidyl ether. Among these compounds, methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, sec-butyl glycidyl ether, tert-butyl glycidyl ether, hexyl glycidyl Alkyl glycidyl ethers of lower and higher alcohols such as ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, more preferably n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether Ether, isobutyl glycidyl ether, sec-butyl glycidyl ether tert-butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, octyl glycidyl ether, lauryl glycidyl ether, more preferably n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, sec -Butyl glycidyl ether, tert-butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, particularly preferably n-butyl glycidyl ether, isobutyl glycidyl ether, sec-butyl glycidyl ether, tert-butyl glycidyl ether, hexyl glycidyl ether Ether, 2-ethylhexyl glycidyl ether, Preferably n- butyl glycidyl ether, isobutyl glycidyl ether, sec- butyl glycidyl ether, tert- butyl glycidyl ether. These compounds may be used alone or in the form of a mixture of two or more. The amount of glycidyl ether (II) used (that is, the amount of side chain (1) introduced) can introduce a sufficient amount of side chain (1) into polyamine compound (I) (that is, sufficient self and drying shrinkage reduction). The amount is not particularly limited as long as the amount can be achieved, but is 0.01 to 0.90 mol, 0.05 to 0.90 mol, 0.10 to 0 per active amine hydrogen of the polyamine compound (I). .85 mole, 0.17 to 0.80 mole, and 0.23 to 0.80 mole in this order.

  In the present invention, the polyamine compound (I) and glycidyl ether (II) are reacted to add and introduce glycidyl ether (II) as a side chain (1) into the polyamine compound (I). The side chain (1) -containing polyamine compound is obtained. The reaction conditions of the polyamine compound (I) and glycidyl ether (II) at this time are such that the reaction proceeds and a sufficient amount of the side chain (1) is polyamine. The conditions are not particularly limited as long as they can be introduced into the compound (I). For example, the polyamine compound (I) and the glycidyl ether (II) are diluted as they are or with a solvent as necessary, and preferably from room temperature to 200 ° C, more preferably from 40 to 150 ° C, still more preferably from 50 to 110 ° C. The reaction is preferably carried out at temperature for 0.5 to 10 hours, more preferably 0.5 to 6 hours. The reaction may be carried out under normal pressure, under pressure, or under reduced pressure, but preferably under normal pressure. At this time, the solvent used as necessary to dissolve / disperse / suspend each compound is not particularly limited, but the polyamine compound (I), glycidyl ether (II) or side chain (1) -containing polyamine compound is used. It is preferably soluble and inert to them. Specifically, alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutyl alcohol, isoamyl alcohol; hydrocarbons such as n-butane, propane, benzene, cyclohexane, naphthalene; acetic acid Esters such as methyl, ethyl acetate, ethyl benzoate, ethyl lactate; polyhydric alcohols such as (poly) ethylene glycol, ethylene glycol monobutyl ether acetate, tetraethylene glycol, (poly) propylene glycol, propylene glycol monobutyl ether and their derivatives Water, alcohols, hydrocarbons, and esters are preferred, especially water, methanol, ethanol, isopropanol, cyclohexane, ethylene glycol. Lumpur, ethylene glycol monobutyl ether, ethyl acetate is preferred. These solvents may be different solvents or the same solvents for the polyamine compound (I), the glycidyl ether (II) and the side chain (1) -containing polyamine compound. The same solvent is preferably used in consideration of the property and the labor of the subsequent solvent removal step. In the reaction, a catalyst may be used to promote the reaction. Such a catalyst is not particularly limited as long as it can promote the reaction, and a known catalyst can be used. Specific examples include titanium catalysts such as tetrabutyl titanate and tetraisopropyl titanate; tin catalysts such as stannous chloride, tin octylate and monobutyltin oxide; acids such as p-toluenesulfonic acid.

  The side chain (1) -containing polyamine compound thus obtained is not particularly limited as long as it is generated by the above-described reaction. Specifically, polyethyleneimine / methylglycidyl ether, polyethyleneimine / ethylglycidyl ether, Polyethyleneimine / propyl glycidyl ether, polyethyleneimine / butyl glycidyl ether, polyethyleneimine / hexyl glycidyl ether, polyethyleneimine / 2-ethylhexyl glycidyl ether, polyethyleneimine / octyl glycidyl ether, polyethyleneimine / lauryl glycidyl ether, polyethyleneimine / stearyl glycidyl ether Polyethyleneimine / alkyl glycidyl ethers; polyethyleneimine / octylphenyl glycidyl ether Polyethyleneimine / nonylphenyl glycidyl ether, polyethyleneimine / laurylphenylglycidyl ether, polyethyleneimine / stearylphenylglycidyl ether and other polyethyleneimine / alkylphenol glycidyl ethers; polyethyleneimine / octylcyclopentylglycidyl ether, polyethyleneimine / octylcyclohexylglycidyl ether, Polyethyleneimine / nonylcyclopentylglycidyl ether, polyethyleneimine / nonylcyclohexylglycidylether, polyethyleneimine / laurylcyclopentylglycidylether, polyethyleneimine / laurylcyclohexylglycidylether, polyethyleneimine / stearylcyclopentylglycidylether Polyethyleneimine / stearylcyclohexyl glycidyl ether, such as polyethyleneimine / alkylcycloalkanol glycidyl ether; polyethyleneimine / octylbenzylglycidylether, polyethyleneimine / nonylbenzylglycidylether, polyethyleneimine / laurylbenzylglycidylether, polyethyleneimine / stearylbenzylglycidylether Such as glycidyl ether of polyethyleneimine / alkylbenzyl alcohol.

  The side chain (1) -containing polyamine compound thus obtained has the following structure in which the active amine hydrogen of the polyamine compound (I) is substituted with the side chain (1):

A side chain (1) -containing polyamine compound having In the present invention, the side chain (1) does not need to be completely substituted with active amine hydrogen, and may be partially substituted as in the above structure. When the side chain (1) -containing polyamine compound according to the present invention is dissolved in water due to the presence of a hydrocarbon group having 1 to 30 carbon atoms which is a hydrophobic group of glycidyl ether (II), the surface tension of water is reduced. By expressing the lowering effect and thereby reducing the tensile force generated between the surface of the cured body and water, self and drying shrinkage can be suppressed. Therefore, the additive for hydraulic materials containing such a side chain (1) -containing polyamine compound can be suitably used for the construction of highly durable concrete.

In the present invention, in the polyamine compound (I), in addition to the side chain (1), as the side chain (2), an oxyalkylene group having 2 to 4 carbon atoms and —COOZ (where Z is a hydrogen atom) , Monovalent metal, divalent metal, ammonium group, organic amine group or — (R ² O) _n —R ³ , where R ² O is one of oxyalkylene groups having 2 to 18 carbon atoms. or an a mixture of two or more, n is a mean addition mol number of the oxyalkylene group ^(R 2 O), the number of 1 to 500, ^{R 3} is a hydrogen atom or 1 to 3 carbon atoms -SO ₃ W (wherein W represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group); and at least one group selected from the group consisting of —SO ₃ W (representing a hydrocarbon group); Furthermore, it can have as a side chain (2). By introducing the side chain (2), adsorption of the polyamine compound to the cement particles occurs, and the surface of the cured body is hydrophobized, so that the tensile force between the cured body and water is lowered, thereby further increasing the drying shrinkage reduction effect. Because it can. In the present specification, the polyamine compound having the side chains (1) and (2) is referred to as “side chain (1,2) -containing polyamine compound”. In the present invention, the side chain (1,2) -containing polyamine compound may be a single side chain (2) introduced into the polyamine compound (I) or two or more types of side chains (2). It may be coexisted in the polyamine compound (I).

  In the present invention, the introduction of the side chain (2) can be achieved by a known method, and is not particularly limited. The produced side chain (1) -containing polyamine compound is an oxyalkylene having 2 to 4 carbon atoms and / or the following formula (1):

And a compound represented by the formula (herein referred to as “compound (III)”). Alternatively, the side chain (1,2) -containing polyamine compound is obtained by first reacting the polyamine compound (I) with oxyalkylene having 2 to 4 carbon atoms and / or the compound (III) of the above formula (1). The reaction product may be further reacted with glycidyl ether (II). The side chain (1,2) -containing polyamine compound thus obtained induces hydrophobization of the cement surface when adsorbed on the cement surface due to the introduction of the side chain (2), and pulls it between water. It exerts the effect of reducing the force, which can further suppress self and drying shrinkage.

  In the present invention, the oxyalkylene having 2 to 4 carbon atoms is not particularly limited, and preferred examples include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, and 2-butene oxide. More preferred are ethylene oxide, propylene oxide, butylene oxide, and even more preferred are ethylene oxide and propylene oxide. These oxyalkylenes may be used alone or in the form of a mixture of two or more or may be used in combination with compound (III) detailed below.

In the above formula (1) representing the compound (III), X ¹ represents an atomic group having a functional group capable of reacting with an amino group, and this group X ¹ reacts with an active amine hydrogen of the polyamine compound (I). Then, the group Y as the side chain (2) is introduced into the polyamine compound (I). Such an atomic group is not particularly limited as long as it has a functional group capable of reacting with an amino group. For example, epoxy, isocyanate, thioisocyanate, (meth) acrylate, aldehyde ketone, halogenated alkyl, halogenated And acyl-derived groups. Of these, epoxy, isocyanate, (meth) acrylate, and alkyl halide are preferable, and epoxy, (meth) acrylate, and alkyl halide are particularly preferable. Y represents COOZ or SO ₃ W, preferably COOZ. In the formula: SO ₃ W representing the substituent “Y”, W represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group (—NH ₃ ), or an organic amine group. In this case, examples of the monovalent metal include lithium, sodium, and potassium, preferably sodium and potassium. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like, preferably calcium and barium. Examples of the organic amine group include groups derived from primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine; Groups derived from secondary amines such as amine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, dibenzylamine and diphenylamine; trimethylamine, triethylamine, tripropyl Groups derived from tertiary amines such as amine, tributylamine, tricyclohexylamine, tribenzylamine and triphenylamine; and ethanolamine, diethanolamine Include groups derived from alkanolamines such as triethanolamine. Among these, alkanolamine groups such as ethanolamine group, diethanolamine group and triethanolamine group, and triethylamine group are preferable. Among these, W is preferably a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and particularly preferably a monovalent metal, a divalent metal or an ammonium group. In the formula: COOZ representing the substituent “Y”, Z represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group (—NH ₃ ), an organic amine group, or — (R ² O) _n —R ^3. Represents. At this time, the monovalent metal, the divalent metal, and the organic amine group are the same as the definition of the substituent “W”, and thus the description thereof is omitted here. In the formula: — (R ² O) _n —R ³ , R ² O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. An oxyalkylene group, more preferably an oxyalkylene group having 2 to 4 carbon atoms. Preferred examples of such oxyalkylene group include oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, oxy1-butene group, oxy2-butene group, and oxystyrene group, but more preferably An oxyethylene group, an oxypropylene group, and an oxybutylene group, still more preferably an oxyethylene group and an oxypropylene group. When a plurality of these oxyalkylene groups are present in one substituent “Z” (that is, n is 2 or more in formula (1)), one oxyalkylene group is one in one substituent “Z”. There may be a kind or a mixture of two or more kinds. When two or more kinds of oxyalkylene groups are present, the addition form may be any of random addition, block addition, alternating addition, and the like. Among these, Z is preferably a hydrogen atom, a monovalent metal, a divalent metal, or — (R ² O) _n —R ³ , and is a monovalent metal, a divalent metal, or — (R ² O) _n —. R ³ is particularly preferred. Also, n is a mean addition mol number of the oxyalkylene group ^(R 2 O), the number of 1 to 500. When n exceeds 500, excessive fluidity (dispersibility) is imparted to the hydraulic material composition, so that it may not be possible to add an amount necessary for self and drying shrinkage suppression. n is preferably 1 to 300, more preferably 1 to 100, and most preferably 1 to 50. R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. In this case, specific examples of the hydrocarbon group having 1 to 3 carbon atoms include methyl, ethyl, propyl, isopropyl and the like.

  Specific examples of such compound (III) include (meth) acrylic acid; (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid, methoxy ( Poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol maleate, methoxy (poly) ethylene glycol (poly) propylene glycol maleate, etc. It is done. These compounds (III) may be used alone or in the form of a mixture of two or more or in combination with the oxyalkylenes detailed above. Among these, (meth) acrylic acid, maleic acid, hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meta ) Acrylate, methoxy (poly) ethylene glycol maleate, methoxy (poly) ethylene glycol (poly) propylene glycol maleate are preferred, especially acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methoxy (poly) ethylene glycol (Meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol maleate, metho Shi (poly) ethylene glycol (poly) propylene glycol maleate are preferred.

  In the present invention, the amount of oxyalkylene and / or compound (III) used is sufficient to react with the polyamine compound (I) or the side chain (1) -containing polyamine compound to obtain the side chain (1,2) -containing polyamine compound. Although it is not particularly limited as long as it can be formed, considering the reactivity with the polyamine compound (I) and the polyamine compound containing the side chain (1), the total amount of oxyalkylene and / or compound (III) used is the polyamine compound. 0.01 to 0.90 mol, more preferably 0.05 to 0.80 mol, even more preferably 0.10 to 0.70 mol, and most preferably 0.000 mol per active amine hydrogen of (I). The amount is preferably 10 to 0.60 mol. In the present invention, it is particularly preferable that the compound (III) does not exist excessively. This is because if there is a large amount of compound (III), poor curing may occur.

  In the above embodiment, the polyamine compound (I) / side chain (1) -containing polyamine compound and the compound (III) are reacted to add and introduce the side chain (2) to the polyamine compound (I). The side chain (1,2) -containing polyamine compound is obtained by the reaction, and the reaction conditions of the polyamine compound (I) / side chain (1) -containing polyamine compound and compound (III) at this time are such that the reaction proceeds. As long as a sufficient amount of the side chain (2) can be introduced into the polyamine compound (I), there is no particular limitation. For example, polyamine compound (I) / side chain (1) -containing polyamine compound and compound (III) Or diluted with a solvent as necessary, preferably dissolved, dispersed or suspended in a solvent, most preferably dissolved in a solvent, preferably from room temperature to 200 ° C. More preferably at a temperature of 40 to 100 ° C., preferably 0.5 to 6 hours, more preferably 0.5 to 4 hours, to the reaction. The reaction may be carried out under normal pressure, under pressure or under reduced pressure, but preferably under normal pressure. At this time, the solvent used as necessary for dissolving / dispersing / suspending each compound is not particularly limited, but polyamine compound (I), / polyamine compound containing side chain (1), compound (III) Alternatively, it is preferable that the polyamine compound containing the side chain (1, 2) can be dissolved and is inactive to these. Specifically, water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutyl alcohol, isoamyl alcohol and other alcohols; n-butane, propane, benzene, cyclohexane, naphthalene and other hydrocarbons; acetic acid Esters such as methyl, ethyl acetate, ethyl benzoate, and ethyl lactate; many (poly) ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, tetraethylene glycol, (poly) propylene glycol, propylene glycol monobutyl ether, etc. For example, water, alcohols, hydrocarbons, and esters, particularly water, methanol, ethanol, isopropanol. Lumpur, cyclohexane, ethylene glycol, ethylene glycol monobutyl ether, ethyl acetate is preferred. These solvents may be different solvents or the same solvents for the polyamine compound (I), the compound (II) and the side chain (1) -containing polyamine compound. The same solvent is preferably used in consideration of the property and the labor of the subsequent solvent removal step. In addition, the solvent used in the reaction between the polyamine compound (I) and the compound (II) and the solvent used in the above reaction may be either the same or different, but the operability In view of the labor of the subsequent solvent removal step, etc., the same solvent is preferably used. Furthermore, in the reaction, a catalyst may be used to promote the reaction. Such a catalyst is not particularly limited as long as it can promote the reaction, and a known catalyst can be used. Specific examples include titanium catalysts such as tetrabutyl titanate and tetraisopropyl titanate; tin catalysts such as stannous chloride, tin octylate and monobutyltin oxide; acids such as p-toluenesulfonic acid.

  In the present invention, in addition to the side chain (1) or the side chains (1) and (2), the side chain (3) is added to the polyamine compound (I) as —COOZ ′ (where Z ′ is 1 to 3). Can be introduced at a rate of 2.4 or less per one side chain (1). In the present specification, the compound having the side chains (1) and (3) and, if necessary, the side chain (2) is simply referred to as “side chain (1,3) -containing polyamine compound”. By introducing such a specific amount of the side chain (3), the adsorption of the polyamine compound to the cement particles occurs, and the surface of the cured body is hydrophobized. Therefore, the tensile force between the cured body and water is lowered, thereby drying shrinkage. This is because the reduction effect can be further increased. In the present invention, the side chain (1,3) -containing polyamine compound may be a single side chain (3) introduced into the polyamine compound (I) or two or more side chains (3 ) May be present in the polyamine compound (I).

  In the present invention, the introduction of the side chain (3) can be achieved by a known method, and is not particularly limited. The produced side chain (1) -containing polyamine compound or side chain (1,2) -containing polyamine compound is represented by the following formula (2):

And a compound represented by the formula (herein referred to as “compound (IV)”). Alternatively, the side chain (1,3) -containing polyamine compound having side chains (1) and (3) is first reacted with the compound (IV) of the above formula (2), after the polyamine compound (I) is reacted. The reaction product may be further prepared by reacting with glycidyl ether (II). The side chain (1,3) -containing polyamine compound thus obtained induces hydrophobicity of the surface of the cured product when adsorbed on the cement surface by introducing such a specific amount of carboxylic acid group, The effect of reducing the tensile force between them is exhibited, whereby self and drying shrinkage can be further suppressed.

  In the side chain (1,3) -containing polyamine compound according to the present invention, the side chain (3) is preferably introduced at a ratio of 2.4 or less per one side chain (1). This is because when the side chain (3) exceeds 2.4 and is introduced into the polyamine compound (I), the amount of the side chain (1) introduced is relatively reduced, and the carboxylic acid-derived Excessive groups are introduced into the polyamine compound (I), resulting in excessive dispersibility of the resulting side chain (1,3) -containing polyamine compound. This is because the drying shrinkage reduction property may be excessively lowered. Considering the drying shrinkage reduction effect of the side chain (1,3) -containing polyamine compound, the amount of the side chain (3) introduced into the polyamine compound (I) is 0.10 with respect to one side chain (1). ˜2.00, more preferably 0.15 to 1.75, and most preferably 0.20 to 1.50.

In the above formula (2) representing the compound (IV), X ¹ is the same as the definition of the substituent “X ¹ ” in the above formula (1), and thus the description thereof is omitted here. Y ′ represents —COOZ ′. In this case, Z ′ represents 1 to 3 hydrocarbon groups. Specific examples of the hydrocarbon group having 1 to 3 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, propyl and isopropyl; cyclic alkyl groups such as cyclopropyl and the like. Of these, linear alkyl groups such as methyl, ethyl and propyl, particularly methyl and ethyl are preferred.

  Specific examples of such compound (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like. These compounds (IV) may be used alone or in the form of a mixture of two or more. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.

  In the present invention, the amount of compound (IV) used is set so as to be present in a predetermined amount with respect to side chain (1) as described above, and contains polyamine compound (I) and side chain (1). Although it will not specifically limit if it is the quantity which can react with a polyamine compound or a side chain (1,2) content polyamine compound and can fully form a side chain (1,3) content polyamine compound, when considering the reactivity with the above-mentioned compound, The amount of compound (IV) used is 0.01 to 0.90 mol, more preferably 0.05 to 0.80 mol, and most preferably 0.05 to 0.80 mol per active amine hydrogen of the polyamine compound (I). It is preferable to be 0.70 mol.

  In the present invention, the side chain-containing polyamine according to the present invention is obtained by reacting the polyamine compound (I), glycidyl ether (II) with oxyalkylene and / or compound (III) and / or compound (IV). A compound is obtained. In this specification, the side chain (1) -containing polyamine compound, the side chain (1,2) -containing polyamine compound, and the side chain (1,3) -containing polyamine compound are collectively referred to as “side chain-containing polyamine compound”. Called. At this time, polyamine compound (I), glycidyl ether (II), oxyalkylene and / or compound (III), and / or compound (IV) are added in the order of polyamine compound (I), compound (II), oxyalkylene. And / or compound (III) and / or compound (IV) are not particularly limited as long as a desired side chain-containing polyamine compound can be obtained by reaction. For example, polyamine compound (I), glycidyl ether (II), oxyalkylene and / or compound (III), and / or compound (IV) are simultaneously added to carry out the reaction; polyamine compound (I) is subjected to glycidyl ether ( II) is reacted and then reacted with oxyalkylene and / or compound (III); polyamine compound (I) is reacted with glycidyl ether (II) and then reacted with compound (IV); polyamine compound ( After reacting I) with oxyalkylene and / or compound (III), the reaction is carried out by adding glycidyl ether (II); after reacting polyamine compound (I) with compound (IV), glycidyl ether ( II) is added to carry out the reaction; to the polyamine compound (I), glycidyl ether Le (II) and compound was added (III) by carrying out the reaction; or polyamine compound (I), etc. The reaction is carried out by adding the glycidyl ether (II) and the compound (IV), may be any. Of these, polyamine compound (I), glycidyl ether (II), oxyalkylene and / or compound (III) are simultaneously added to carry out the reaction; polyamine compound (I), glycidyl ether (II), oxyalkylene and / Or compound (III) and / or a method in which compound (IV) is added simultaneously to carry out the reaction; after reacting glycidyl ether (II) with polyamine compound (I), oxyalkylene and / or compound (III) A method of reacting polyamine compound (I) with glycidyl ether (II) and then reacting with compound (IV); after reacting polyamine compound (I) with compound (IV), glycidyl A method of carrying out the reaction by adding ether (II); and a polyamine compound After the (I) was reacted with oxyalkylene and / or the compound (III), a method of performing the reaction by the addition of the glycidyl ether (II) is preferably used.

  The reaction conditions of polyamine compound (I) / side chain (1) -containing polyamine compound / side chain (1,2) -containing polyamine compound and compound (IV) are such that the reaction proceeds and a sufficient amount of side chain is obtained. There is no particular limitation as long as (2) can be introduced into the polyamine compound (I). For example, the reaction conditions of the polyamine compound (I) / side chain (1) -containing polyamine compound and the compound (III) are the same. And preferably used.

  The polyamine compound (I) / side chain (1) -containing polyamine compound into which the side chain (2) and / or the side chain (3) is introduced according to the present invention is a (meth) acrylic acid introduced into the side chain as necessary. The ester moiety can be hydrolyzed.

  Such a polyamine compound (I) / side chain (1) into which the side chain (2) and / or the side chain (3) are introduced by hydrolyzing the (meth) acrylic acid ester moiety introduced into the side chain. This is because, when the contained polyamine compound is stored in an aqueous solution, it is possible to suppress performance degradation caused by hydrolysis of the (meth) acrylic acid ester portion that occurs with time.

  In the present invention, the hydrolysis of the (meth) acrylic acid in the side chain (2) and / or the side chain (3) can be achieved by a known method, and is not particularly limited, but specifically, for example, the hydrolysis temperature Is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. The hydrolysis time is preferably 0.5 hours or more, more preferably 1 hour or more, although it depends on the temperature and pH of hydrolysis for complete hydrolysis.

  The side chain-containing polyamine compound thus obtained is not particularly limited as long as it is generated by the above-described reaction, and specifically, polyethyleneimine / methylglycidyl ether, polyethyleneimine / methylglycidyl ether / (meth). Acrylic acid, polyethyleneimine / methyl glycidyl ether / methyl (meth) acrylate, polyethylene imine / methyl glycidyl ether / ethyl (meth) acrylate, polyethylene imine / methyl glycidyl ether / propyl (meth) acrylate, polyethylene imine / methyl glycidyl Ether / (meth) acrylic acid 2-hydroxyethyl, polyethyleneimine / methyl glycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / methyl glycidyl ether / (Meth) acrylic acid / ethyl (meth) acrylate, polyethyleneimine / ethyl glycidyl ether, polyethyleneimine / ethyl glycidyl ether / (meth) acrylic acid, polyethyleneimine / ethyl glycidyl ether / methyl (meth) acrylate, polyethylene Imine / ethyl glycidyl ether / ethyl (meth) acrylate, polyethyleneimine / ethyl glycidyl ether / propyl (meth) acrylate, polyethyleneimine / ethyl glycidyl ether / 2-hydroxyethyl (meth) acrylate, polyethyleneimine / ethyl glycidyl ether / (Meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / ethyl glycidyl ether / (meth) acrylic acid / ethyl (meth) acrylate, polyethylene / Propyl glycidyl ether, polyethyleneimine / propyl glycidyl ether / (meth) acrylic acid, polyethyleneimine / propyl glycidyl ether / methyl (meth) acrylate, polyethyleneimine / propyl glycidyl ether / ethyl (meth) acrylate, polyethyleneimine / Propyl glycidyl ether / propyl (meth) acrylate, polyethylene imine / propyl glycidyl ether / 2-hydroxyethyl (meth) acrylate, polyethylene imine / propyl glycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethylene imine / Propyl glycidyl ether / (meth) acrylic acid / ethyl (meth) acrylate, polyethyleneimine / butyl glycidyl ether, polyethyleneimine / Butyl glycidyl ether / (meth) acrylic acid, polyethyleneimine / butyl glycidyl ether / methyl (meth) acrylate, polyethyleneimine / butyl glycidyl ether / ethyl (meth) acrylate, polyethyleneimine / butyl glycidyl ether / (meth) acrylic acid Propyl, polyethyleneimine / butyl glycidyl ether / 2-hydroxyethyl (meth) acrylate, polyethyleneimine / butyl glycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / butyl glycidyl ether / (meth) acrylic Acid / ethyl (meth) acrylate, polyethyleneimine / hexylglycidyl ether, polyethyleneimine / hexylglycidyl ether / (meth) acrylic acid, polyethyleneimid / Hexyl glycidyl ether / methyl (meth) acrylate, polyethyleneimine / hexyl glycidyl ether / ethyl (meth) acrylate, polyethylene imine / hexyl glycidyl ether / propyl (meth) acrylate, polyethylene imine / hexyl glycidyl ether / (meth) 2-hydroxyethyl acrylate, polyethyleneimine / hexylglycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / hexylglycidyl ether / (meth) acrylic acid / ethyl (meth) acrylate, polyethyleneimine / 2-ethylhexyl glycidyl ether, polyethyleneimine / 2-ethylhexyl glycidyl ether / (meth) acrylic acid, polyethyleneimine / 2-ethylhexyl glycidyl Ether / methyl (meth) acrylate, polyethyleneimine / 2-ethylhexyl glycidyl ether / ethyl (meth) acrylate, polyethyleneimine / 2-ethylhexyl glycidyl ether / propyl (meth) acrylate, polyethyleneimine / 2-ethylhexyl glycidyl ether / (Meth) acrylic acid 2-hydroxyethyl, polyethyleneimine / 2-ethylhexyl glycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / 2-ethylhexyl glycidyl ether / (meth) acrylic acid / (meth) Ethyl acrylate, polyethyleneimine / octylglycidyl ether, polyethyleneimine / octylglycidyl ether / (meth) acrylic acid, polyethyleneimine / octylglycidyl Ether / methyl (meth) acrylate, polyethyleneimine / octyl glycidyl ether / ethyl (meth) acrylate, polyethylene imine / octyl glycidyl ether / propyl methacrylate, polyethyleneimine / octyl glycidyl ether / (meth) acrylic acid 2 -Hydroxyethyl, polyethyleneimine / octylglycidyl ether / (meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / octylglycidyl ether / (meth) acrylic acid / ethyl (meth) acrylate, polyethyleneimine / lauryl glycidyl ether , Polyethyleneimine / lauryl glycidyl ether / (meth) acrylic acid, polyethyleneimine / lauryl glycidyl ether / methyl (meth) acrylate, polyethylene / Lauryl glycidyl ether / (meth) acrylate ethyl, polyethyleneimine / lauryl glycidyl ether / propyl (meth) acrylate, polyethyleneimine / lauryl glycidyl ether / 2-hydroxyethyl (meth) acrylate, polyethyleneimine / lauryl glycidyl ether / (Meth) acrylic acid / methyl (meth) acrylate, polyethyleneimine / lauryl glycidyl ether / (meth) acrylic acid / ethyl (meth) acrylate, and the like. In addition to the above examples, instead of polyethyleneimine, an ethylene oxide adduct of polyethyleneimine (for example, ethylene oxide adduct of polyethyleneimine / butyl glycidyl ether / (meth) acrylic acid), ethyleneimine ethylene oxide and propylene oxide of polyethyleneimine Those substituted with an adduct (for example, ethylene oxide and propylene oxide adduct of polyethyleneimine / butyl glycidyl ether / (meth) acrylic acid, etc.) are also included in the side chain-containing polyamine compound according to the present invention.

  The additive for hydraulic materials of the present invention is suitably used for hydraulic materials. This is because the side chain-containing polyamine compound that constitutes the hydraulic material additive of the present invention reduces the surface tension of water due to the presence of hydrophobic groups, and the cement surface when adsorbed on the cement surface by introduction of carboxylic acid. This is because the tensile force between water is reduced by inducing the hydrophobization of water, and self and drying shrinkage can be efficiently reduced by these effects.

  The additive for hydraulic material of the present invention has only one type of the side chain (1) -containing polyamine compound, the side chain (1,2) -containing polyamine compound, or the side chain (1,3) -containing polyamine compound. Or even two or more types of side chain (1) -containing polyamine compounds, side chain (1,2) -containing polyamine compounds, or side chain (1,3) -containing polyamine compounds; Alternatively, two or more side chain (1) -containing polyamine compounds, one or two or more side chain (1,2) -containing polyamine compounds, or one or more side chain (1,3) -containing polyamine compounds are used. , Or a combination of them as appropriate.

  It is also effective to further improve the dispersibility of cement particles by combining the hydraulic material additive of the present invention and a dispersant. Accordingly, a second aspect of the present invention relates to an additive composition for hydraulic material comprising at least one additive for hydraulic material and a dispersant of the present invention. In the present invention, the additive for hydraulic material may be used alone or in the form of a mixture of two or more.

  The dispersant that can be used in the present invention is not particularly limited, and known dispersants can be used. Specifically, an alkenyl ether monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as 3-methyl-3-buten-1-ol as disclosed in JP-A-62-68806. , Unsaturated carboxylic acid monomers, and copolymers comprising monomers copolymerizable with these monomers, or salts thereof, various sulfonic acid dispersants having a sulfonic acid group in the molecule, Known dispersants such as various polycarboxylic acid-based dispersants having a polyoxyalkylene chain and a carboxyl group in the molecule can be used. Examples of the sulfonic acid dispersant include lignin sulfonate; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonate; aminoaryl sulfonic acid-phenol-formaldehyde condensate and the like. Examples thereof include sulfonic acid type (see JP-A-1-113419). Examples of the polycarboxylic acid dispersant include a copolymer of a polyalkylene glycol mono (meth) acrylate ester compound and a (meth) acrylic acid compound and / or a salt thereof as the component (a), ( b) Copolymer of polyalkylene glycol mono (meth) allyl ether compound and maleic anhydride and / or its hydrolyzate and / or salt thereof as component b) Polyalkylene glycol mono (meth) allyl as component (c) A dispersant for cement comprising a copolymer of an ether compound and a maleic ester of a polyalkylene glycol compound and / or a salt thereof (see JP-A-7-267705); a poly (meth) acrylic acid as component A Copolymer of alkylene glycol ester and (meth) acrylic acid (salt), specified as B component Concrete admixture comprising a specific surfactant as C component (see Japanese Patent No. 2508113); polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono ( A copolymer comprising (meth) allyl ether, (meth) allylsulfonic acid (salt), (meth) acrylic acid (salt) (see JP-A-62-216950); polyethylene (propylene) of (meth) acrylic acid A copolymer comprising glycol ester, (meth) allylsulfonic acid (salt), (meth) acrylic acid (salt) (see JP-A-1-226757); polyethylene (propylene) glycol ester of (meth) acrylic acid, (Meth) allylsulfonic acid (salt Alternatively, a copolymer comprising p- (meth) allyloxybenzenesulfonic acid (salt) and (meth) acrylic acid (salt) (see Japanese Patent Publication No. 5-36377); polyethylene glycol mono (meth) allyl ether and maleic acid Copolymer with (salt) (see JP-A-4-149056); polyethylene glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol Mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, a copolymer comprising an α, β-unsaturated monomer having an amide group in the molecule (see JP-A-5-170501); polyethylene glycol mono (Meth) allyl ether, polyethylene glycol mono (meth) acrylate, (meth) acrylic acid Copolymer comprising alkyl ester, (meth) acrylic acid (salt), (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) (see JP-A-6-191918) A copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or a hydrolyzate thereof or a salt thereof (see JP-A-5-43288); polyethylene glycol monoallyl ether, maleic acid and monomers thereof A copolymer comprising a monomer copolymerizable with a monomer or a salt thereof or an ester thereof (see Japanese Patent Publication No. 58-38380); a polyalkylene glycol mono (meth) acrylate ester monomer, (meth) acrylic acid Copolymers comprising monomers and monomers copolymerizable with these monomers (Japanese Patent Publication No. 59-18) 338); a copolymer comprising a (meth) acrylic acid ester having a sulfonic acid group and a monomer copolymerizable therewith if necessary (see Japanese Patent Application Laid-Open No. 62-119147) An esterification reaction product of a copolymer of an alkoxy polyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having an alkenyl group at the terminal (see JP-A-6-271347); alkoxy polyalkylene glycol mono An esterification reaction product of a copolymer of allyl ether and maleic anhydride and a polyoxyalkylene derivative having a hydroxyl group at the terminal (see JP-A-6-298555); a polyalkylene glycol monoester monomer; (Meth) acrylic acid monomers, unsaturated dicarboxylic acid monomers and (meta Copolymer with one or more monomers selected from allyl sulfonic acid monomers (see JP-A-7-223852); monomers having an oxyalkylene group and unsaturated carboxylic acids A polycarboxylic acid copolymer produced by copolymerizing a monomer component containing a monomer with a thiol chain transfer agent having a hydrocarbon group having 3 or more carbon atoms No. 128738).

  Moreover, as a polycarboxylic acid type dispersing agent, the following general formula (3):

In the ^formula, R 4, ^{R 5} and ^{R 6} each independently represent a hydrogen atom or a methyl group; s is an integer from 0 to 2; ^{R 7} O is 2 to 18 carbon atoms Represents one or a mixture of two or more oxyalkylene groups; u represents the average number of moles added of the oxyalkylene group (R ⁷ O), is a number from 1 to 300; and R ⁸ is a hydrogen atom Or a hydrocarbon group having 1 to 30 carbon atoms,
The structural unit (Va) represented by the following formula (5):

In the ^formula, R ^{14, R 15} and ^{R 16} are each independently a hydrogen atom, a methyl group or _- 'represents a group, this _{time, V' (CH 2) q} COOV a hydrogen atom, a monovalent Represents a metal, a divalent metal, an ammonium group or an organic amine group, and q is an integer of 0 to 2; and V represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. , COOV ′ and COOV are two or more, two of these may form an anhydride,
And a polycarboxylic acid-based dispersant (A) containing the structural unit (VI) represented by the following general formula (4):

In the ^formula, R ^{9, R 10} and ^{R 11} each independently represent a hydrogen atom or a methyl group; x is an integer from 0 to ^{2; R 12} O is 2 to 18 carbon atoms Represents one or a mixture of two or more oxyalkylene groups; y represents the average number of moles added of the oxyalkylene group (R ¹² O), is a number from 1 to 300; and R ¹³ is a hydrogen atom Or a hydrocarbon group having 1 to 30 carbon atoms,
A polycarboxylic acid-based dispersant (B) containing the structural unit (Vb) represented by the formula (5) and the structural unit (VI) represented by the above formula (5) as essential structural units, JP-A-7-53645 As described in JP-A-8-208769 and JP-A-8-208770, hydrophilic graft polymers obtained by graft polymerization of unsaturated carboxylic acid monomers to polyether compounds are suitable. Among these, it is preferable to use the polycarboxylic acid dispersant (A) or the polycarboxylic acid dispersant (B). The polycarboxylic acid dispersant (A) and the polycarboxylic acid dispersant (B) may be used alone or in combination of two or more.

  The polycarboxylic acid dispersant (A) is a polymer containing the structural unit (Va) and the structural unit (VI) represented by the general formula (3) as essential structural units. It may contain a structural unit derived from another copolymerizable monomer (e). Each of these structural units in the polycarboxylic acid dispersant (A) may be one kind or two or more kinds.

  In the polycarboxylic acid dispersant (A), the ratio of the structural unit (Va) to the structural unit (VI) (structural unit (Va) / structural unit (VI)) (mass%) is 1 It is preferable that it is -99 / 99-1. Moreover, as a total ratio (mass%) of the structural unit (Va) and the structural unit (VI) in the polycarboxylic acid-based dispersant (A), 50 to 50 of the entire polycarboxylic acid-based dispersant (A). 100 mass% is preferable and 70-100 mass% is more preferable.

  The polycarboxylic acid dispersant (B) is a polymer containing the structural unit (Vb) and the structural unit (VI) represented by the general formula (4) as essential structural units. It may contain a structural unit derived from another copolymerizable monomer (e). Each of these structural units in the polycarboxylic acid dispersant (B) may be one kind or two or more kinds.

  In the polycarboxylic acid-based dispersant (B), the structural unit (Vb) and the structural unit (VI) each occupy 1% by mass or more of all the structural units, and the proportion of the structural unit (Vb). Is preferably 50 mol% or less of all the structural units. When the proportion of the structural unit (Vb) is less than 1% by mass, the content of the oxyalkylene group contained in the polycarboxylic acid dispersant (B) is too small, while the proportion of the structural unit (VI) is 1 mass. If it is less than%, the content of the carboxyl group contained in the polycarboxylic acid dispersant (B) is too small, and the dispersibility tends to decrease. In addition, since the unsaturated (poly) alkylene glycol ether monomer has low polymerizability, in order to obtain a highly dispersible polycarboxylic acid dispersant (B) in a high yield, the structural unit (Vb ) Is preferably 50 mol% or less of all the structural units. In addition, as a total ratio (mass%) of the structural unit (Vb) and the structural unit (VI) in the polycarboxylic acid-based dispersant (B), 50 to 50% of the entire polycarboxylic acid-based dispersant (B). 100 mass% is preferable and 70-100 mass% is more preferable.

  Alternatively, a commercially available cement dispersant may be used. 70 (lignin sulfonic acid compound polyol composite dispersant, manufactured by Pozzolith Corporation), FC-900 (polycarboxylic acid dispersant, manufactured by Nippon Shokubai Co., Ltd.), HW-1 (polycarboxylic acid dispersant, Inc. (Made by Nippon Shokubai). In addition, the said well-known cement dispersing agent may be used independently, or may be used with the form of 2 or more types of mixtures.

  In the present invention, the blending mass ratio of the additive for hydraulic material and the dispersant is not particularly limited as long as the desired drying shrinkage reduction effect and dispersibility can be achieved, and the additive for hydraulic material and cement to be used are used. Although it varies depending on differences in the type, blending, and test conditions of the dispersant, it is preferably 0.5: 99.5 to 99.5: 0.5, more preferably 5:95 to 95: 5, and particularly preferably 10: 90-95: 5, most preferably 20: 80-95: 5. At this time, when the blending ratio of the additive for hydraulic material exceeds 99.5% by mass of the whole, the effect of the dispersant is not sufficiently exhibited, and the fluidity is lowered and the workability may be affected. . On the contrary, when the mixing ratio of the additive for hydraulic material is less than 0.5% by mass of the total, the amount of the additive for hydraulic material is too small, and the self-drying shrinkage of the hydraulic material, particularly the concrete member. May not be sufficiently reduced.

  The hydraulic material additive of the present invention may be used as it is in the form of an aqueous solution, or dried after neutralization with a divalent metal hydroxide such as calcium or magnesium to obtain a polyvalent metal salt. Or may be used after being powdered by supporting it on an inorganic powder such as silica-based fine powder and drying it.

  The additive for hydraulic material of the present invention can be used for various hydraulic materials, that is, hydraulic materials other than cement such as cement and gypsum. As a hydraulic composition containing a hydraulic material, water, and the cement admixture of the present invention, and further containing fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) as needed, cement paste Mortar, concrete and plaster are preferred.

  Among the additive compositions for hydraulic materials, an additive composition using cement as the hydraulic material is the most common, and such additive composition is the additive for hydraulic materials of the present invention. , Cement and water as essential components. Such an additive composition is also one aspect of the present invention.

  Examples of the cement used in the additive composition of the present invention include Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate-resistant and their respective low alkali types), various mixed cements (blast furnace cement, silica cement). , Fly ash cement), white Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low heat generation cement (low heat generation blast furnace) Cement, fly ash mixed low heat generation type blast furnace cement, belite high content cement), ultra high strength cement, cement-based solidified material, eco-cement (cement made from municipal waste incineration ash, sewage sludge incineration ash) ), And blast furnace slag, flyer Gerhard, cinder ash, clinker ash, husk ash, silica fume, silica powder, a fine powder and gypsum limestone powder may be added. In addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., the aggregates are siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia. Refractory aggregate such as can be used.

In the additive composition of the present invention, the unit water amount per 1 m ³ , the amount of cement used, and the water / cement ratio are unit water amount 100 to 185 kg / m ³ , cement amount used 250 to 800 kg / m ³ , water / cement. The ratio (mass ratio) is preferably 0.1 to 0.7, and more preferably, the unit water amount is 120 to 175 kg / m ³ , the cement amount used is 270 to 800 kg / m ³ , and the water / cement ratio (mass ratio). = 0.2 to 0.65 is recommended, and can be used widely from poor blends to rich blends. Both high-strength concrete with a large amount of unit cement and poor blended concrete with a unit cement amount of 300 kg / m ³ or less. It is valid.

  As a mixing ratio of the additive for hydraulic material of the present invention in the additive composition of the present invention, for example, when used for mortar or concrete using hydraulic cement, 0.001 to 20 mass of cement mass % Is preferable. If the amount is less than 0.001% by mass, shrinkage reduction performance may not be obtained. Conversely, if the amount exceeds 20.0% by mass, the curing of the hydraulic material may be easily delayed. More preferably, it is 0.001-10 mass%, More preferably, it is 0.005-5 mass%, Most preferably, it is 0.01-3 mass%.

  The additive composition of the present invention is also effective for ready-mixed concrete, concrete for secondary concrete products (precast concrete), centrifugal molded concrete, vibration compacted concrete, steam-cured concrete, shotcrete, etc. High fluidity of medium fluidity concrete (concrete with slump value of 22-25cm), high fluidity concrete (concrete with slump value of 25cm or more, slump flow value of 50-70cm), self-filling concrete, self-leveling material, etc. It is also effective for required mortar and concrete.

  Furthermore, the additive composition of the present invention can contain other known cement additives (materials) as exemplified in the following (1) to (20).

  (1) Water-soluble polymer substance: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer; methyl Nonionic cellulose ethers such as cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and hydroxypropyl cellulose; polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose A part of or all of the hydroxyl groups of the alkylated or hydroxyalkylated derivatives of the above are a hydrophobic substituent having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, a sulfonic acid group or Polysaccharide derivatives substituted with an ionic hydrophilic substituent containing such a salt as a partial structure; yeast glucan, xanthan gum, β-1.3 glucans (both linear and branched) For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; Copolymers of acrylic acid having groups and quaternary compounds thereof.

  (2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

  (3) retarder: oxycarboxylic such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and inorganic salts or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. Acids: monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, oligosaccharides such as dextrin, polysaccharides such as dextran, etc. Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin; aminotri (methylenephos Acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts, alkaline earth metal salts and other phosphonic acids and their derivatives etc.

  (4) Early strengthening agent / accelerator: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.

  (5) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.

  (6) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, and alkylene oxide adducts thereof.

  (7) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.

  (8) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

  (9) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as 2-ethylhexyl ether and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) oxy such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1 − Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylenic alcohol such as tin-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene (Poly) oxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyls such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate salts; (poly) oxyethylene stearyl phosphates, etc. Sialic sharp emission alkyl phosphate esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide.

  (10) Alcohol-based antifoaming agent: octyl alcohol, 2-ethylhexyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like.

  (11) Amide antifoaming agent: acrylate polyamine and the like.

  (12) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.

  (13) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.

  (14) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

  (15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether , Polyoxyethylene alkyl (phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenylsulfosuccinic acid, α-olefin sulfonate, and the like.

  (16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide and propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as amine having 6 to 30 carbon atoms, lauric acid and stearic acid. Polyalkylene oxide derivatives; having an alkyl group or an alkoxy group as a substituent Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionics Surfactant; various amphoteric surfactants.

  (17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt, wax and the like.

  (18) Rust inhibitor: nitrite, phosphate, zinc oxide and the like.

  (19) Crack reducing agent: polyoxyalkyl ether and the like.

  (20) Expansion material: Ettlingite, coal, etc.

  Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, strength enhancers, self-leveling agents, colorants, fungicides and the like. The known cement additives (materials) can be used in combination.

  These other known cement additives (materials) may be used alone or in the form of a mixture of two or more. In addition, the content of other known cement additives (materials) when other known cement additives (materials) are used is not particularly limited, but is preferably 0. It is 1-90 mass%, More preferably, it is 0.5-70 mass%.

  In the additive composition of the present invention, particularly preferred embodiments of components other than cement and water include the following 1) to 8).

  1) (a) A combination that essentially comprises two components of the hydraulic material additive of the present invention and (b) an oxyalkylene antifoaming agent. The blending mass ratio of the (b) oxyalkylene antifoaming agent is preferably 0.01 to 200% by mass with respect to the (a) additive for hydraulic material.

  2) (a) A combination that essentially comprises two components of the hydraulic material additive of the present invention and (b) lignin sulfonate. The blending mass ratio of (a) hydraulic material additive to (b) lignin sulfonate is preferably 99.5 / 0.5 to 0.5 / 99.5, and 98/2. ~ 20/80 is more preferred.

  3) A combination that essentially comprises two components of (a) the hydraulic material additive of the present invention and (b) a polycarboxylic acid-based dispersant. The blending mass ratio of the additive for hydraulic material (a) and the polycarboxylic acid dispersant (b) is preferably 99.5 / 0.5 to 0.5 / 99.5, 98 / 2 to 20/80 is more preferable.

  4) A combination comprising essentially three components: (a) the additive for hydraulic material of the present invention, (b) lignin sulfonate, and (c) an oxyalkylene antifoaming agent. The blending mass ratio of (a) hydraulic material additive to (b) lignin sulfonate is preferably 99.5 / 0.5 to 0.5 / 99.5, and 98/2. ~ 20/80 is more preferred. The blending mass ratio of the (c) oxyalkylene antifoaming agent is 0.01 to 200% by mass with respect to the total mass of the hydraulic material additive (a) and the lignin sulfonate salt (b). Is preferred.

  5) A combination comprising essentially three components: (a) the additive for hydraulic material of the present invention, (b) a polycarboxylic acid-based dispersant, and (c) an oxyalkylene-based antifoaming agent. The blending mass ratio of the additive for hydraulic material (a) and the polycarboxylic acid dispersant (b) is preferably 99.5 / 0.5 to 0.5 / 99.5, 98 / 2 to 20/80 is more preferable. The blending mass ratio of the (c) oxyalkylene antifoaming agent is 0.01 to 200 with respect to the total mass of the hydraulic material additive (a) and the polycarboxylic acid dispersant (b). Mass% is preferred.

  6) (a) A combination that essentially comprises two components of the hydraulic material additive of the present invention and (b) a material separation reducing agent. As a material separation reducing agent, various thickeners such as nonionic cellulose ethers, an average addition of a hydrophobic substituent having a hydrocarbon chain with 4 to 30 carbon atoms and an alkylene oxide with 2 to 18 carbon atoms as a partial structure A compound having a polyoxyalkylene chain having 2 to 300 moles added can be used. The mixing mass ratio of the additive for hydraulic material (a) and the material separation reducing agent (b) is preferably 10/90 to 99.99 / 0.01, and preferably 50/50 to 99.9. /0.1 is more preferable. The additive composition comprising this combination is suitable as high fluid concrete, self-filling concrete, and self-leveling material.

  7) (a) Combination of 2 components of the hydraulic material of the present invention and (b) retarder essential. As the retarder, oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, phosphonic acids such as aminotri (methylenephosphonic acid), and the like can be used. . Of these, oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt) are particularly preferred. In addition, the blending mass ratio of the additive for hydraulic material (a) and the retarder (b) is preferably 50/50 to 99.9 / 0.1, more preferably 70/30 to 99/1. preferable.

  8) A combination comprising two components, (a) hydraulic material additive of the present invention and (b) accelerator. As the accelerator, soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfate, formic acid and calcium formate, and the like can be used. The blending mass ratio of the hydraulic material additive (a) to the accelerator (b) is preferably 10/90 to 99.9 / 0.1, more preferably 20/80 to 99/1. preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the present specification, unless otherwise specified, “%” represents “mass%” and “part” represents “part by mass”.

Production Example 1
Epomin (registered trademark) SP-018 (polyethyleneimine with a molecular weight of 1,800, manufactured by Nippon Shokubai Co., Ltd.) was added to a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser. The reaction vessel was purged with nitrogen under stirring and heated to 90 ° C. under a nitrogen atmosphere. Next, 92.6 parts of butyl 2,3-epoxypropyl ether (butyl glycidyl ether, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours, and then the temperature was maintained at 90 ° C. for 1.5 hours. Next, the temperature was lowered to 50 ° C., and 6.1 parts of methyl acrylate was added dropwise in 0.5 hours, and then the temperature was maintained at 50 ° C. for 1 hour, and butyl 2,3-epoxypropyl ether and methyl acrylate were maintained. The addition reaction of was terminated. Next, after adding 9.5 parts of NaOH aqueous solution adjusted to 30 wt% and 340.5 parts of pure water, temperature was raised to 60 degreeC and methyl acrylate was hydrolyzed over 1 hour. After completion of the hydrolysis, the temperature was lowered to 20 ° C. or lower, 19.2 parts of acetic acid was added, and the pH was adjusted to 8.4 to obtain an aqueous polymer 1 solution of the present invention.

Production Example 2
Into a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 48.8 parts of Epomin (registered trademark) SP-018 was charged, and the inside of the reaction vessel was purged with nitrogen under stirring. Heated to 90 ° C. under nitrogen atmosphere. Next, 95.3 parts of butyl 2,3-epoxypropyl ether was added dropwise over 3 hours, and then the temperature was maintained at 90 ° C. for 1.5 hours. Next, the temperature was lowered to 50 ° C., and 5.8 parts of methyl acrylate was added dropwise over 0.5 hour, and the temperature was maintained at 50 ° C. for 1 hour, followed by butyl 2,3-epoxypropyl ether and methyl acrylate. The addition reaction of was terminated. Next, 9.0 parts of NaOH aqueous solution adjusted to 30 wt% and 341.0 parts of pure water were added, and then the temperature was raised to 60 ° C. to hydrolyze methyl acrylate over 1 hour. After completion of the hydrolysis, the temperature was lowered to 20 ° C. or lower, and 19.2 parts of acetic acid was added to adjust the pH to 8.4 to obtain an aqueous polymer 2 solution of the present invention.

Production Example 3
51. Epomin (registered trademark) SP-030 (polyethyleneimine having a molecular weight of about 3,000, manufactured by Nippon Shokubai Co., Ltd.) in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube and a reflux condenser. 2 parts were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 90 ° C. in a nitrogen atmosphere. Next, after 92.6 parts of butyl 2,3-epoxypropyl ether was added dropwise over 3 hours, the temperature was maintained at 90 ° C. for 1.5 hours. Next, the temperature was lowered to 50 ° C., and 6.2 parts of methyl acrylate was added dropwise over 0.5 hour, and then the temperature was maintained at 50 ° C. for 1 hour, and butyl 2,3-epoxypropyl ether and methyl acrylate were maintained. The addition reaction of was terminated. Next, after adding 9.6 parts of NaOH aqueous solution adjusted to 30 wt% and 340.4 parts of pure water, the temperature was raised to 60 ° C. to hydrolyze methyl acrylate over 1 hour. After completion of the hydrolysis, the temperature was lowered to 20 ° C. or lower, 22.2 parts of acetic acid was added and the pH was adjusted to 8.0 to obtain an aqueous polymer 3 solution of the present invention.

Production Example 4
A glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser was charged with 129.3 parts of Epomin (registered trademark) SP-030 and 100.7 parts of pure water, and reacted with stirring. The inside of the container was replaced with nitrogen and heated to 60 ° C. in a nitrogen atmosphere. Next, 17.4 parts of an acrylic acid aqueous solution adjusted to 75% by mass was added dropwise over 0.5 hours, and then the temperature was maintained at 60 ° C. for 2 hours. Next, the temperature was raised to 90 ° C., 102.7 parts of butyl 2,3-epoxypropyl ether was added dropwise over 2 hours, and then maintained at 90 ° C. for 2 hours. The addition reaction of 3-epoxypropyl ether was completed. Next, the temperature was lowered to 70 ° C. and 140.0 parts of pure water was added, and then the temperature was lowered to 20 ° C. or lower to obtain an aqueous polymer 4 solution of the present invention.

Production Example 5
Into a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 60.1 parts of Epomin (registered trademark) SP-018 was charged, and the inside of the reaction vessel was purged with nitrogen under stirring. Heated to 90 ° C. under nitrogen atmosphere. Next, 82.8 parts of α-olefin epoxide AOE X24 having 12 to 14 carbon atoms (manufactured by Daicel Chemical Industries, Ltd., hereinafter referred to as AOE X24) was added dropwise over 3 hours, followed by 1.5 hours. The temperature was maintained at Next, the temperature was lowered to 50 ° C., and 7.2 parts of methyl acrylate was added dropwise over 0.5 hour, and then the temperature was maintained at 50 ° C. for 1 hour to complete the addition reaction of AOE X24 and methyl acrylate. . Next, 15.3 parts of NaOH aqueous solution adjusted to 30 wt% and 334.7 parts of pure water were added, and then the temperature was raised to 60 ° C. to hydrolyze methyl acrylate over 1 hour. After completion of the hydrolysis, the temperature was lowered to 20 ° C. or lower, 30.0 parts of acetic acid was added, and the pH was adjusted to 7.4 to obtain an aqueous polymer 5 solution of the present invention.

Production Example 6
Into a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 62.5 parts of Epomin SP-018 was charged, and the inside of the reaction vessel was purged with nitrogen under stirring. Heated to 90 ° C. Next, 80.0 parts of 1,2-epoxyhexane (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours, and then the temperature was maintained at 90 ° C. for 1.5 hours. Next, the temperature was lowered to 50 ° C., 7.5 parts of methyl acrylate was added dropwise over 0.5 hour, and then maintained at 50 ° C. for 1 hour, and 1,2-epoxyhexane and methyl acrylate were added. The reaction was terminated. Next, after adding 11.6 parts of NaOH aqueous solution adjusted to 30 wt% and 338.4 parts of pure water, temperature was raised to 60 degreeC and methyl acrylate was hydrolyzed over 1 hour. After completion of hydrolysis, the temperature was lowered to 20 ° C. or lower, and 19.2 parts of acetic acid was added to adjust the pH to 8.4 to obtain an aqueous polymer 6 solution of the present invention.

Examples 1-6, Comparative Examples 1-4
Table 1 shows monomer compositions of polymers (1) to (6) produced in the same manner as in Production Examples 1 to 6. In Table 1, the amount of butyl glycidyl ether (hereinafter referred to as “BGE”), AOE X24 (hereinafter referred to as “AOE”) and 1,2-epoxyhexane (hereinafter referred to as “EpHx”) is polyamine. It is represented by the number of moles per active amine hydrogen of compound (I), and the amount of compound (IV) introduced is represented by the molar ratio of compound (IV) to BGE, AOE and EpHx. Moreover, the general physical properties and drying shrinkage reduction effect of the mortar were evaluated as follows, and the results are shown in Table 2 below.

1. Mortar kneading Mortar kneading was performed as follows. 225 g of a predetermined amount of polymer weighed and diluted with water, 450 g of ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.) and standard sand for cement strength test (JIS R 5201-1997, Annex 2, 5.1.3) Regulation: Cement Association) 1350 g of mortar was kneaded according to JIS R 5201-1997 using a Hobart mortar mixer: Model No. N-50 (manufactured by Hobart). In Table 2, the addition amount of the polymer is shown by mass% with respect to the cement.

  Moreover, the amount of mortar air was adjusted using the antifoamer (polyoxyalkylene glycol alkyl ether type) as needed so that the amount of mortar air might be 5.0-10.0 vol%.

2. Measurement of mortar flow value The mortar flow value was measured according to the method described in JIS R 5201-1997, and compared with the flow value ratio. The flow value ratio is the ratio of the mortar flow value at the time of addition of the polymer to the mortar flow value of the mortar (reference mortar) to which no polymer is added, as shown by the following formula (1). Indicates.

3. Measurement of the amount of mortar air The amount of mortar air was measured using a 500 ml graduated cylinder in accordance with JIS A 1174 (Method of testing the unit volume and mass of polymer cement mortar that has not yet solidified, and the test method based on the mass of air (mass method)). Carried out.

4). Evaluation of drying shrinkage reduction The mortar was kneaded by the same method as in item 1 above.

  Next, preparation of a mortar specimen (4 × 4 × 16 cm) for evaluating drying shrinkage reduction was performed according to JIS R 1129.

  Silicone grease was applied to the mold in advance to stop the water and make it easy to remove the mold. In addition, gauge plugs were attached to both ends of the specimen. The formwork into which the mortar obtained by kneading was poured was put in a container, sealed and stored at 20 ° C., and initial curing was performed. The mold was removed after 1 day, and the silicon grease adhering to the specimen was washed with water using a scourer and then cured in still water at 20 ° C. for 6 days (water curing).

  A dial gauge (manufactured by West Japan Testing Machine Co., Ltd.) was used in accordance with JIS A 1129. After wiping off the water on the surface of the specimen cured for 6 days in still water with a paper towel, the length was measured immediately, and the length at this point was used as a reference. Thereafter, the sample was stored for 28 days in a constant temperature and humidity chamber set at a temperature of 20 ° C. and a humidity of 60%, and the time was measured appropriately. At this time, the length change ratio is the ratio of the shrinkage amount of the polymer-added mortar to the shrinkage amount of the reference mortar, as shown by the following formula (2). The smaller the value, the more the shrinkage can be reduced.

5. Method for measuring mortar setting time Mortar kneading was carried out in the same manner as in item 1 above.

  The setting time was measured using a penetration resistance test apparatus according to ASTM C 403 / C 403M-99. The setting start time and setting end time of the polymer-added mortar and the reference mortar were measured.

6). Method for measuring mortar compressive strength The compressive strength was measured according to JIS A 1108-1999. Mortar was poured into a cylindrical specimen mold having an inner diameter of 50 mm and a height of 100 mm, and sealing curing was performed at 20 ° C. After 1 day, the mold was removed, followed by curing (water curing) in still water at 20 ° C. On the 7th and 28th days after the start of curing, the specimens were taken out and the compressive strength was measured. At this time, the compressive strength ratio is the ratio of the compressive strength of the polymer-added mortar to the compressive strength of the reference mortar, as shown by the following formula (3), and the higher the value, the higher the compressive strength.

  From the results shown in Table 2 above, when the polymers 1 to 4 of the present invention were compared with the polymers 5 and 6 (Comparative Examples 1 to 3), the same amount of polymer was added, and the drying was of the same degree with a short setting time. It showed shrinkage reduction. Further, in the polymers 5 and 6, when the polymer addition amount was increased, the material separation (polymer 5) and the decrease in compressive strength (polymer 6) due to excessive dispersibility were shown, but in the polymers 1 and 3 according to the present invention, There was no effect on material separation and compressive strength due to the added amount. Therefore, in these polymers 1 and 3, it can be expected that any drying shrinkage reduction property can be obtained without affecting the material separation and compressive strength of the mortar.

Examples 7 to 9 and Comparative Examples 5 to 7: Concrete Evaluation This example uses concrete for the purpose of evaluating the drying shrinkage reduction property and the general physical properties of concrete as follows. It was done. Each material was weighed so that the amount of kneading became 40 L according to the concrete composition shown below, and kneading of the material was performed using a biaxial forced kneading mixer. The cement is Taiheiyo Cement Co., Ltd. and Sumitomo Osaka Cement Co., Ltd. In addition, ordinary Portland cement (specific gravity 3.16) manufactured by Ube Mitsubishi Cement Co., Ltd. was used in an evenly mixed manner. At this time, Ogasa land sand (specific gravity 2.64, coarse particle rate 2.75) is used for fine aggregate, and Ome hard crushed stone (specific gravity 2.54, coarse particle rate 6.65) is used for coarse aggregate. used. Further, using a high-performance AE water reducing agent and an antifoaming agent, the concrete slump value was adjusted to 18 ± 2 cm, and the air amount was adjusted to 4.0 ± 1.0%. The high performance AE water reducing agent and antifoaming agent used were as follows.

High performance AE water reducing agent: Polycarboxylic acid type Antifoaming agent: Polyoxyalkylene glycol alkyl ether type <Concrete mix>
Unit cement amount: 350 kg / m ³
Unit water volume: 175 kg / m ³
Unit fine aggregate amount: 833 kg / m ³
Unit coarse aggregate amount: 903 kg / m ³
(Water-cement ratio (W / C): 50.0%, fine aggregate ratio (s / a): 49.0%)
<Kneading ingredients>
Fine aggregate, cement and coarse aggregate were put into a mixer and kneaded for 10 seconds, and then the rotation was stopped. Water containing a polymer, an antifoaming agent and a high performance AE water reducing agent was added and kneaded for 90 seconds, and then the concrete was taken out of the mixer and evaluated.

<Evaluation of fresh concrete>
About the obtained fresh concrete, the measurement of the slump value, the amount of air, and the setting time was implemented with the following method.

Slump value: JIS A 1101-1998
Air volume: JIS A 1128-1998
Setting time: JIS A 1147-2001
<Evaluation of drying shrinkage reduction>
The obtained fresh concrete was put into a 10 × 10 × 40 cm specimen mold with a gauge pin, demolded after initial curing at 20 ° C. for 1 day, and further cured in water at 20 ° C. for 6 days to reduce drying shrinkage. Evaluation of sex started.

  The evaluation of the drying shrinkage reduction was carried out according to JIS A 1129-3 (Mortar and concrete length change test method Part 3: Dial gauge method).

  As comparative controls at this time, polymers 5 to 0.65 and 0.75% by mass with respect to cement and 0.13% by mass of a high-performance AE water reducing agent to cement were used, respectively.

  These results are shown in Table 3 below. In Comparative Example 6, since significant material separation occurred, the setting time and drying shrinkage reduction evaluation could not be performed.

  From the results shown in Table 3 above, it can be seen that good drying shrinkage reduction can be obtained by adding the polymer of the present invention. In addition, the polymers 2 and 3 (Examples 7 to 9) of the present invention have the same properties of fresh concrete as the standard polymer 5 (Comparative Examples 5 and 6), particularly the same setting time, and high drying shrinkage. Reduced. Further, since the polymer 3 showed the same dry shrinkage reducing property with a smaller addition amount than the polymer 5, it can be seen that the polymer 3 has a high dry shrinkage reducing property. In addition, when 0.75% by mass of polymer 5 was added to cement, material separation occurred due to excessive dispersibility, whereas 1.0% by mass of polymers 2 and 3 was added to cement. However, since it is necessary to use in combination with a high-performance AE water reducing agent in order to achieve a predetermined slump value, the polymer of the present invention has a low influence on dispersibility by addition. Therefore, it is expected that the polymer of the present invention has little influence on the general physical properties of concrete due to the addition, and can easily obtain any drying shrinkage reduction property.

Examples 10-12, Comparative Example 8: Drying shrinkage reduction evaluation using blast furnace slag mixed cement mortar This example is for the purpose of evaluating the drying shrinkage reduction of hydraulic materials using blast furnace slag mixed cement. Was performed as follows.

<Kneading mortar>
The mortar for evaluation was kneaded as follows. 450.5 g of ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.), 368.6 g of blast furnace slag fine powder (manufactured by Nippon Steel Blast Furnace Cement Co., Ltd., brain value 4,000) and 1350 g of standard sand for cement strength test, Hobart type Mortar mixer: put into Model No. N-50 (made by Hobart), kneaded at the first speed for 30 seconds, stopped kneading, weighed a predetermined amount of polymer, diluted with water, 409.5g over 10 seconds And put it in. After the addition, the kneading was stopped at the first speed for 30 seconds, and then the kneading was stopped and scraped off for 20 seconds. Next, kneading was performed at a first speed for 120 seconds to obtain an evaluation mortar.

  Moreover, the amount of mortar air was adjusted using the antifoamer (polyoxyalkylene glycol alkyl ether type) as needed so that the amount of mortar air might be 5.0-10.0 vol%.

<Measurement of mortar air volume>
The mortar air amount was measured using a 500 ml graduated cylinder according to JIS A 1174 (unit volume mass test method of polymer cement mortar not yet solidified and test method based on mass of air amount (mass method)).

<Evaluation of drying shrinkage reduction>
Evaluation of mortar drying shrinkage reduction was carried out as follows.

  Preparation of a mortar specimen (4 × 4 × 16 cm) for evaluating drying shrinkage reduction was carried out according to JIS R 1129.

  Silicone grease was applied to the mold in advance to stop the water and make it easy to remove the mold. In addition, gauge plugs were attached to both ends of the specimen. The formwork into which the mortar obtained by kneading was poured was put in a container, sealed and stored at 20 ° C., and initial curing was performed. The mold was removed after 1 day, and the silicon grease adhering to the specimen was washed with water using a scourer and then cured in still water at 20 ° C. for 6 days (water curing).

    A dial gauge (manufactured by West Japan Testing Machine Co., Ltd.) was used in accordance with JIS A 1129. After wiping off the water on the surface of the specimen cured for 6 days in still water with a paper towel, the length was measured immediately, and the length at this point was used as a reference. Thereafter, the sample was stored for 28 days in a constant temperature and humidity chamber set at a temperature of 20 ° C. and a humidity of 60%, and the time was measured appropriately. At this time, the length change ratio is a ratio of the shrinkage amount of the polymer-added mortar to the shrinkage amount of the reference mortar, as shown by the following formula. As a comparative control at this time, a commercially available polyoxyalkylene glycol type shrinkage reducing agent (reducing agent 1) added at 2.0% by mass to the cement was used.

  These results are shown in Table 4.

  From the results shown in Table 4 above, the polymer of the present invention is equivalent to or better than the addition amount of 1/2 of the standard reducing agent 1, and in particular, the shrinkage reduction property of polymer 3 is equivalent to or better than the addition amount of 1/4. Even when blast furnace slag fine powder mixed cement is used, a good drying shrinkage reduction effect is exhibited.

Examples 13 to 15 and Comparative Examples 9 to 10: Drying shrinkage reduction evaluation in mortar using blast furnace slag mixed cement This example is for the purpose of evaluating self shrinkage reduction of a hydraulic material using blast furnace slag mixed cement. The mortar was used as follows.

<Kneading mortar>
The mortar for evaluation was kneaded as follows. Ordinary Portland cement (Pacific Cement Co., Ltd.) 504.9 g, blast furnace slag fine powder (Nippon Steel Blast Furnace Cement Co., Ltd., Brain value 4,000) 413.1 g, Hobart mortar mixer: Model No. N-50 (Hobart And then kneaded at a first speed for 5 seconds, weighed a predetermined amount of polymer, diluted with water, and added 275.4 g over 15 seconds while kneading, and kneaded for 10 seconds. Stopped. Subsequently, 1350 g of standard sand for cement strength test (specified in 5.1.3 of JIS R 5201-1997 Annex 2; Cement Association) was added over 30 seconds. After the addition, the kneading was stopped at the first speed for 60 seconds, and then the kneading was stopped and scraped off for 20 seconds. Next, kneading was performed at a first speed for 120 seconds to obtain an evaluation mortar.

  At this time, the polycarboxylic acid-based high-performance AE water reducing agent and antifoaming agent (polyoxyalkylene) are used as necessary so that the mortar flow value and the mortar air amount are 200 ± 20 mm and 5.0 to 10.0 vol%, respectively Glycol alkyl ether type) was used to adjust the mortar flow and the amount of air.

<Measurement of mortar flow>
The mortar flow was measured according to the method described in JIS R 5201-1997.

<Measurement of mortar air volume>
The mortar air amount was measured using a 500 ml graduated cylinder according to JIS A 1174 (unit volume mass test method of polymer cement mortar not yet solidified and test method based on mass of air amount (mass method)).

<Evaluation of self-shrinkage reduction>
The self-shrinkage reduction property was evaluated by measuring the self-shrinkage strain as follows.

Self-shrinkage strain was measured using a strain gauge (model: KCM-70-120-H4, manufactured by Kyowa Denki Co., Ltd.). Simultaneously with this strain measurement, the setting time was measured by penetration resistance measurement, and the setting start time was set as the starting point of the strain measurement. The setting time was measured by measuring the penetration resistance value in a room set at a temperature of 20 ± 2 ° C. according to ASTM C 403 / C 403M-99. That is, the mortar obtained by using the same method as that described above was packed in a polypropylene container (caliber × lower diameter × height = 91 × 84 × 127 mm) in two portions, and 4 hours after water injection. Measurement of penetration resistance value was started. The time when the penetration resistance value became 3.5 N / mm ² was set as a starting point for measuring the self-shrinkage strain.

  The apparatus shown in FIG. 1 was used for the measurement of the self-shrinkage strain. As the container, a polypropylene container having a caliber × lower diameter × height = 91 × 84 × 127 mm was used. In addition, silicon grease was applied in advance to the inside of the container to prevent adhesion between the container and the mortar so that the mold could be easily removed. After the container was filled with the mortar obtained by kneading as described above, the container was covered with a polyvinylidene chloride sheet and stored at 20 ± 2 ° C., and at the same time, shrinkage strain was measured. As comparative controls at this time, a commercially available polyoxyalkylene glycol type shrinkage reducing agent (reducing agent 1) was added in an amount of 2.0% by mass to the cement and a high performance AE water reducing agent was added in an amount of 0.085% by mass to the cement. Each one was used.

  The results are shown in Table 5.

  The results shown in Table 5 above show that a high self-shrinkage reduction effect can be obtained by adding the polymer according to the present invention. In addition, since the amount of addition of 1/4 to 1/2 of the standard reducing agent 1 shows the same or better self-shrinkage reduction, the ratio of water to binder using blast furnace slag fine powder mixed cement It is expected that a high self-shrinkage reducing effect can be obtained even with a low hydraulic material.

It is a figure explaining the apparatus used for the measurement of a self contraction distortion.

Claims (10)

  The additive for hydraulic materials containing the polyamine compound which has a polyamine structure as a main chain and has a group derived from glycidyl ether having a hydrocarbon group having 1 to 30 carbon atoms as a side chain (1) as an essential component.   The additive for hydraulic material according to claim 1, wherein the side chain (1) is a group derived from a glycidyl ether of a lower or higher alcohol having a hydrocarbon group having 1 to 30 carbon atoms. The polyamine compound has, as a side chain (2), an oxyalkylene group having 2 to 4 carbon atoms; —COOZ (where Z is a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, an organic amine group, or — ( R ² O) _n —R ³ , wherein R ² O represents one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms, and n represents an oxyalkylene group (R ² O ) Represents an average added mole number of 1 to 500, R ³ represents a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms); and —SO ₃ W (W is a hydrogen atom) The additive for hydraulic materials according to claim 1 or 2, further comprising at least one group selected from the group consisting of: a monovalent metal, a divalent metal, an ammonium group, and an organic amine group. The side chain (2) represents —COOZ (where Z represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, an organic amine group, or — (R ² O) _n —R ³ ). ² O represents one or a mixture of two or more oxyalkylene groups having 2 to 18 carbon atoms, n represents the average number of moles added of the oxyalkylene group (R ² O), and is a number from 1 to 500. The additive for hydraulic material according to claim ³ , wherein R ³ represents a hydrogen atom or a hydrocarbon having 1 to 3 carbon atoms.   The polyamine compound further includes —COOZ ′ (wherein Z ′ represents a hydrocarbon group having 1 to 3 carbon atoms) as a side chain (3). The additive for hydraulic materials described.   The additive for hydraulic material according to claim 5, wherein the side chain (3) is present at a ratio of 2.4 or less per one side chain (1).   The additive for hydraulic materials according to any one of claims 1 to 6, wherein the main chain is a polyalkyleneimine.   The additive composition for hydraulic materials containing the additive for hydraulic materials of any one of Claims 1-7, and a dispersing agent.   A hydraulic material composition comprising the hydraulic material additive composition according to claim 8 and a hydraulic material.   The hydraulic material composition according to claim 9, comprising blast furnace slag fine powder as an essential component.