Composition, cement admixture and hydraulic composition

Abstract

Provided is a composition containing a polymer (A), which contains a structural unit (a) represented by general formula (I) and a structural unit (b) represented by general formula (II), and a halogen atom, wherein the content of the halogen atom is 0.7-1300 mass ppm inclusive. (Symbols in the formulae are as defined in the description.)

Description

Composition, cement admixture and hydraulic composition

[0001] The present invention relates to a composition, a cement admixture and a hydraulic composition.

[0002] Hydraulic compositions (also called concrete compositions), such as cement paste, mortar, and concrete, are used in various fields, including civil engineering and construction. Hydraulic compositions are prepared by mixing a hardening material, such as cement, an aggregate, such as sand, gravel, or stone, with water. Generally, hydraulic compositions begin to harden from the time they are mixed and prepared, and therefore tend to lose fluidity over time. Therefore, when a hydraulic composition prepared in a manufacturing plant or the like is transported to a construction site and poured, hardening progresses, resulting in a decrease in fluidity and a significant decrease in workability.

[0003] In order to solve the above problems, it is effective to reduce the viscosity of the hydraulic composition and suppress the increase in viscosity over time. One method for doing so is to increase the water / cement ratio, but this method has problems such as separation of aggregates and cements in the hydraulic composition, and a decrease in the strength of the set product of the hydraulic composition due to evaporation of water during setting of the hydraulic composition. Furthermore, with the above method, it is difficult to sufficiently suppress the increase in viscosity over time, i.e., the decrease in fluidity over time.

[0004] In light of this background, various additives for hydraulic compositions have been proposed. For example, Patent Document 1 proposes a copolymer for cement admixtures obtained by polymerizing a specific unsaturated polyalkylene glycol ether monomer and an unsaturated monocarboxylic acid monomer, each having a limited chain length, under specific conditions. It is described that the copolymer exhibits excellent dispersibility even in a high water reduction range where the water / cement ratio is low. Patent Document 2 also proposes a concrete admixture containing (a) a copolymer of a specific alkenyl ether and maleic acid or a salt thereof, and (b) a copolymer obtained by polymerizing a monomer mixture containing (a) a specific monomer such as a (meth)acrylic acid ester of methoxypolyethylene glycol and (b) a specific monomer such as (meth)acrylic acid. It is described that the concrete admixture can impart stable fluidity to concrete.

[0005] Japanese Patent Application Laid-Open No. 2001-220417 Japanese Patent Application Laid-Open No. 2001-172068

[0006] If it were possible to improve the fluidity of a hydraulic composition and suppress its decrease over time without increasing the water / cement ratio, i.e., if it were possible to simultaneously improve the fluidity of a hydraulic composition and suppress its decrease over time, workability during application would be improved and a decrease in strength of the set hydraulic composition could be suppressed. However, the techniques described in Patent Documents 1 and 2 were not sufficiently satisfactory in both improving fluidity and suppressing its decrease over time. Therefore, an object of the present invention is to provide a composition that can improve the fluidity of a hydraulic composition and suppress its decrease over time, and a cement admixture containing the same. Another object of the present invention is to provide a hydraulic composition in which the decrease over time in fluidity is suppressed.

[0007] As a result of investigations conducted by the inventors to solve the above problems, they found that a composition containing a polymer having a specific structure and a specific amount of halogen atoms can improve the fluidity of a hydraulic composition and suppress a decrease in fluidity over time, and thus completed the present invention.

[0008] That is, the present invention provides the following items [1] to

[12] : [1] A composition comprising a polymer (A) including a structural unit (a) represented by the following general formula (I) and a structural unit (b) represented by the following general formula (II), and a halogen atom, wherein the content of the halogen atoms is 0.7 ppm by mass or more and 1,300 ppm by mass or less. (In general formula (I), R １ and R ２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ may be bonded to each other to form a ring structure. Ａ and R Ｂ each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ O- may be the same or different from each other. Ｂ O- may be the same or different from each other. O and p each independently represent 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond. (In general formula (II), R ２１ , R ２２ , and R ２３each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together. X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. M represents a hydrogen atom, an alkali metal atom, or ammonium. * represents a bond. [2] The composition according to [1] above, wherein the halogen atom is a chlorine atom. [3] The composition according to [1] above or [2] above, comprising a compound (B) represented by the following general formula (III) in an amount of 0.7 ppm by mass or more and 1000 ppm by mass or less. (In general formula (III), Y １ and Y ２ each independently represent a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. h and i each independently represent an integer of 1 to 4.) [4] The composition according to any one of the above [1] to [3], wherein the polymer (A) contains a structural unit (c) represented by the following general formula (IV) in an amount of 5 mol % or less relative to the structural unit (a): (In general formula (IV), Y ３ and Y ４ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. j and k each independently represent an integer of 1 to 4. * represents a bond. [5] In the general formula (I), R ３ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ [6] The composition according to any one of the above [1] to [4], wherein each independently represents a hydrogen atom or a methyl group. ４ , R ５ , R ６ , and R ７represents a hydrogen atom, and o and p are 0. [7] In the general formula (I), R Ａ and R Ｂ each independently represent an ethylene group, a propylene group, or a butylene group. [8] The composition according to any of [1] to [7] above, wherein the content of the halogen atoms is 0.8 ppm by mass or more and 1,000 ppm by mass or less. [9] A method for producing the composition according to any of [1] to [8] above, comprising the step of heating a mixed solution containing an unsaturated polyalkylene glycol monomer, a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, and a compound (B-1) represented by the following general formula (VI) to obtain the polymer (A), wherein the content of halogen atoms in the mixed solution is 0.7 ppm by mass or more and 1,300 ppm by mass or more: (In general formula (VI), Y ５ and Y ６ each independently represent a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. 1 and m each independently represent an integer of 1 to 4.)

[10] A cement admixture comprising the composition according to any one of the above items [1] to [8].

[11] A hydraulic composition comprising the composition according to any one of the above items [1] to [8].

[12] A composition comprising a polymer (C) represented by the following general formula (V) and halogen atoms, wherein the content of the halogen atoms is 0.7 ppm by mass or more and 1,300 ppm by mass or less: (In general formula (V), R ３１ and R ３２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. Ｃ and R Ｄ each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ O- may be the same or different from each other. Ｄ O- may be the same or different from each other, q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.

[0009] According to the present invention, it is possible to provide a composition that can improve the fluidity of a hydraulic composition and suppress a decrease in fluidity over time, and a cement admixture using the same. It is also possible to provide a hydraulic composition in which a decrease in fluidity over time is suppressed.

[0010] First, the definitions of the notations used in this specification are shown below. "(Meth)acrylic" is a general term for acrylic and methacrylic. Similarly, "(meth)acrylate" is a general term for acrylate and methacrylate, and "(meth)allyl" is a general term for allyl and methallyl. Furthermore, "acid (salt)" is a general term for acids and their acid salts. The weight average molecular weight in this specification is the weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0011] [First composition (D1)] The first composition according to an embodiment of the present invention comprises a polymer (A) including a structural unit (a) represented by the following general formula (I) and a structural unit (b) represented by the following general formula (II), and a halogen atom, wherein the content of the halogen atoms is 0.7 ppm by mass or more and 1300 ppm by mass or less. In this specification, the first composition (D1) may also be referred to as "composition (D1)."

[0012]

[0013]

[0014] The composition (D1) according to the embodiment of the present invention contains a polymer (A) having a specific structure and a specific amount of halogen atoms, and thereby can improve the fluidity of the hydraulic composition and suppress a decrease in fluidity over time.

[0015] <Polymer (A)> The polymer (A) contains the structural unit (a) represented by the above general formula (I) and the structural unit (b) represented by the above general formula (II). By containing the structural unit (a), the polymer (A) can impart sufficient fluidity to the hydraulic composition and suppress a decrease in fluidity over time, even when the water / cement ratio in the hydraulic composition is low, i.e., when the water content in the hydraulic composition is small. Furthermore, by containing the structural unit (b), the polymer (A) can enable the composition (D1) to be adsorbed to cement and cement hydrate, thereby enabling the effect imparted by the structural unit (a) to be exerted.

[0016] The content of the polymer (A) in the composition (D1) is preferably 0.5 to 80 mass%, more preferably 1 to 50 mass%, and even more preferably 3 to 40 mass%, from the viewpoint of efficiently obtaining the effects of the present invention.

[0017] <Structural Unit (a)> The structural unit (a) is represented by the above general formula (I). In general formula (I), R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.

[0018] R １ and R２ Examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0019] R １ and R ２ Examples of the alkanoyl group having 2 to 6 carbon atoms represented by the formula (I) include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pentanoyl group, an isopentanoyl group, a pivaloyl group, a hexanoyl group, a cyclopropylacetyl group, a cyclobutaneacetyl group, and a cyclopentaneacetyl group.

[0020] From the viewpoint of ease of manufacturing, R １ and R ２ is preferably a hydrogen atom, a methyl group, or an acetyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0021] R ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms.

[0022] R ３ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0023] R ３ Examples of the alkanoyloxy group having 2 to 6 carbon atoms represented by the formula (I) include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pentanoyloxy group, an isopentanoyloxy group, a pivaloxy group, a cyclopropylacetyloxy group, a cyclobutaneacetyloxy group, and a cyclopentaneacetyloxy group.

[0024] From the viewpoint of the polymerizability of the monomer, R ３is preferably a hydrogen atom, a methyl group, or an acetoxy group, more preferably a hydrogen atom or an acetoxy group, and even more preferably a hydrogen atom.

[0025] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0026] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0027] From the viewpoint of ease of production and polymerizability of the monomer, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0028] R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ may be bonded to each other to form a ring structure. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１Examples of the ring structure formed by bonding together include a single ring such as a cyclopropane ring, a cyclopentane ring, or a cyclohexane ring; a condensed ring such as a norbornane ring; a tetrahydrofuran ring, a pyrrolidine ring, or a tetrahydrothiophene ring.

[0029] R Ａ and R Ｂ R each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ and R Ｂ Examples of the alkylene group having 2 to 6 carbon atoms represented by include an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, an isopentylene group, a hexylene group, and a cyclohexylene group.

[0030] From the viewpoint of availability and polymerizability, R Ａ and R Ｂ is preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group.

[0031] A plurality of oxyalkylene-R Ａ From the viewpoint of ease of production, a plurality of oxyalkylene-R Ａ It is preferable that the O- are the same as each other. Ｂ From the viewpoint of ease of production, a plurality of oxyalkylene-R Ｂ It is preferred that the O- are the same as each other.

[0032] o and p each independently represent 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond.

[0033] From the viewpoint of polymerizability, o and p are preferably 0. From the viewpoint of polymerizability, m and n are preferably integers of 10 to 50, more preferably integers of 10 to 40, and even more preferably integers of 15 to 30.

[0034] In one embodiment of the present invention, from the viewpoint of improving the fluidity of the hydraulic composition and suppressing the decrease in fluidity over time, R ３ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ In another embodiment of the present invention, from the viewpoint of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time, it is preferable that R ４ , R ５ , R ６ , and R ７ represents a hydrogen atom, and o and p are preferably 0.

[0035] From the viewpoint of imparting adsorption properties to cement, the content of structural unit (a) in polymer (A) is preferably 1 to 50 mol %, more preferably 2 to 45 mol %, and even more preferably 5 to 40 mol %, based on all structural units constituting polymer (A). The content of each structural unit in polymer (A) in this specification is a value calculated from a 1H-NMR spectrum, and can be calculated by comparing the integral value of the spectrum derived from structural unit (a) appearing around 4.0 to 4.5 ppm with the integral value of the spectrum derived from structural unit (b) appearing around 1.5 to 2.5 ppm. Details of the measurement method can follow the method described in the Examples.

[0036] <Structural Unit (b)> The structural unit (b) is represented by the above general formula (II). In general formula (II), R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together.

[0037] R２１ , R ２２ , and R ２３ The alkyl group having 1 to 6 carbon atoms represented by is the same as the above-mentioned R １ and R ２ The same groups as those exemplified as the "alkyl group having 1 to 6 carbon atoms" represented by the formula: can be exemplified.

[0038] R ２１ , R ２２ , and R ２３ Examples of the alkyloxy group having 1 to 6 carbon atoms represented by include an ethoxy group, a propoxy group, a butoxy group, an isobutyloxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group, and a cyclohexyloxy group.

[0039] R ２１ , R ２２ , and R ２３ Examples of the alkenyl group having 2 to 6 carbon atoms represented by include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, an iso-3-hexenyl group, and a cyclohexenyl group.

[0040] R ２１ , R ２２ , and R ２３ Examples of the alkenyloxy group having 2 to 6 carbon atoms represented by include an ethenyloxy group, a propenyloxy group, a butenyloxy group, an isobutenyloxy group, a pentenyloxy group, an isopentenyloxy group, a hexenyloxy group, and a cyclohexenyloxy group.

[0041] R ２１ , R ２２ , and R ２３ Examples of the aralkyl group having 7 to 12 carbon atoms represented by include a methylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a pentylphenyl group, an isopentylphenyl group, a hexylphenyl group, an isohexylphenyl group, and a cyclohexylphenyl group.

[0042] R ２１ , R ２２ , and R ２３Examples of the aralkyloxy group having 7 to 12 carbon atoms represented by the formula (I) include a benzyloxy group, a methylphenylmethoxy group, a dimethylphenylmethoxy group, a trimethylphenylmethoxy group, a tetramethylphenylmethoxy group, a pentamethylphenylmethoxy group, an ethylphenylmethoxy group, a propylphenylmethoxy group, a butylphenylmethoxy group, and a naphthylmethoxy group.

[0043] R ２１ , R ２２ , and R ２３ Examples of the aryl group having 6 to 12 carbon atoms represented by include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0044] R ２１ , R ２２ , and R ２３ Examples of the aryloxy group having 6 to 12 carbon atoms represented by include a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group.

[0045] R ２１ , R ２２ , and R ２３ The alkanoyloxy group having 2 to 6 carbon atoms represented by the above-mentioned R ３ The same groups as those exemplified as the "alkanoyloxy group having 2 to 6 carbon atoms" represented by the formula: can be exemplified.

[0046] From the viewpoint of availability and the number of acid groups per unit mass, R ２１ , R ２２ , and R ２３ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0047] X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. From the viewpoints of availability and handling, X is preferably a carboxylate group.

[0048] M represents a hydrogen atom, an alkali metal atom, or ammonium. From the viewpoint of the stability of the polymer (A), M is preferably an alkali metal atom or ammonium, more preferably an alkali metal atom, and even more preferably sodium.

[0049] * represents a bond.

[0050] The structural unit (b) represented by general formula (II) is preferably a structure derived from a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule. Examples of polymerizable monomers having a polymerizable unsaturated group and an acid group in one molecule include (meth)acrylic acid (salt), crotonic acid (salt), isocrotonic acid (salt), senecioic acid (salt), and oleic acid (salt). From the viewpoints of polymerizability and availability, the structural unit (b) is preferably a structure derived from (meth)acrylic acid (salt).

[0051] From the viewpoint of imparting adsorptivity to cement particles, the content of the structural unit (b) in the polymer (A) is preferably 20 to 90 mol %, more preferably 30 to 90 mol %, and even more preferably 35 to 90 mol %, based on all structural units constituting the polymer (A).

[0052] <Structural Unit (c)> The polymer (A) may contain a structural unit (c) represented by the following general formula (IV). When the polymer (A) contains the structural unit (c), the hydration reaction of cement in the hydraulic composition is accelerated, and the hardening of the hydraulic composition is accelerated. On the other hand, the structural units (a) and (b) contained in the polymer (A) suppress the hardening of the hydraulic composition. Therefore, the hardening rate of the hydraulic composition can be controlled by appropriately adjusting the amounts of the structural units (a), (b), and (c) in the polymer (A).

[0053]

[0054] In general formula (IV), Y ３ and Y ４ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ３ and Y ４ is preferably a chlorine atom.

[0055] j and k each independently represent an integer of 1 to 4. From the viewpoint of ease of production, j and k are preferably 1 or 2, and more preferably 1.

[0056] From the viewpoint of effectively maintaining fluidity, the content of the structural unit (c) in the polymer (A) is preferably 5 mol % or less, more preferably 4 mol % or less, and even more preferably 3 mol % or less, relative to the structural unit (a) represented by general formula (I). From the viewpoint of effectively maintaining fluidity, the content of the structural unit (c) in the polymer (A) is preferably 0.01 mol % or more, more preferably 0.02 mol % or more, and even more preferably 0.1 mol % or more, relative to the structural unit (a) represented by general formula (I). That is, the content of the structural unit (c) in the polymer (A) is preferably 0.01 to 5 mol %, more preferably 0.02 to 4 mol %, and even more preferably 0.1 to 3 mol %, relative to the structural unit (a) represented by general formula (I).

[0057] From the viewpoint of effectively maintaining fluidity, the content of the structural unit (c) in the polymer (A) is preferably 0.005 to 2.5 mol %, more preferably 0.01 to 2.25 mol %, and even more preferably 0.1 to 2 mol %, based on all structural units constituting the polymer (A).

[0058] <Other Structural Units> The polymer (A) may contain structural units other than the structural units (a), (b), and (c). When the polymer (A) contains other structural units, the content of the other structural units in the polymer (A) is preferably more than 0 mol and not more than 20 mol%, more preferably more than 0 mol and not more than 10 mol%, and even more preferably more than 0 mol and not more than 5 mol%, based on the total structural units constituting the polymer (A).

[0059] <Weight Average Molecular Weight of Polymer (A)> The weight average molecular weight of the polymer (A) is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time.

[0060] <Method for producing polymer (A)> The method for producing the polymer (A) of the present invention is not particularly limited as long as the effects of the present invention can be obtained. The polymer (A) can be produced, for example, by polymerizing a solution containing an unsaturated polyalkylene glycol monomer and a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule using a polymerization initiator. A solution containing further components other than those described above may also be used as long as the effects of the present invention are not impaired.

[0061] The unsaturated polyalkylene glycol monomer used in the production of the polymer (A) may be a compound (C) represented by the general formula (V) described below.

[0062] Examples of the polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, which is used to produce the polymer (A), include the polymerizable monomers having a polymerizable unsaturated group and an acid group in one molecule described in the above <Structural Unit (b)>.

[0063] Examples of the polymerization method include known methods such as solution polymerization and bulk polymerization. Among these, solution polymerization is preferred. Examples of the solvent used in solution polymerization include water, alcohol solvents such as methyl alcohol and ethyl alcohol, hydrocarbon solvents such as toluene and n-hexane, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as tetrahydrofuran. The solvents may be used alone or in combination of two or more.

[0064] The polymerization initiator may be a thermally decomposable polymerization initiator, a redox polymerization initiator, or the like. Examples of thermally decomposable polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, peroxides such as hydrogen peroxide and peracetic acid, and azo compounds such as 2,2'-azobisisobutyronitrile (AIBN). Examples of redox polymerization initiators include hydrogen peroxide and L-ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

[0065] When carrying out the polymerization, a chain transfer agent may be used as necessary. Examples of the chain transfer agent include 2-mercaptoethanol, 3-mercaptopropionic acid, n-octanethiol, phosphorous acid (salt), and sulfurous acid (salt). The chain transfer agents may be used alone or in combination of two or more.

[0066] The reaction conditions for polymerization can be appropriately selected depending on the monomers, polymerization method, solvent, polymerization initiator, etc. The reaction temperature is preferably 0° C. or higher, more preferably 30° C. or higher, and is preferably 150° C. or lower, more preferably 120° C. or lower.

[0067] The concentration of each component during polymerization can be appropriately selected depending on the monomer, polymerization method, solvent, polymerization initiator, etc. used, but it is preferable to adjust each component so that the solid content concentration after completion of polymerization is 2% by mass or more, more preferably 5% by mass or more. If the solid content concentration after completion of polymerization is 5% by mass or more, the amount of composition (D1) added to the hydraulic composition can be reduced, which is economically advantageous. The solid content concentration here means the mass ratio of nonvolatile components to the total mass, calculated using an infrared moisture meter, etc.

[0068] The polymer (A) may be stored in the solution used in the polymerization in the same state after polymerization. However, when storing the polymer in the solution used in the polymerization, it is preferable to adjust the pH of the solution used in the polymerization to 5 or more and store the polymer (A) in the solution, in order to avoid deterioration of handleability due to gelation of the solution, etc. The pH can be adjusted using inorganic salts such as hydroxides and carbonates of alkali metals, alkaline substances such as ammonia and organic amines, etc. The pH adjusters may be used alone or in combination of two or more. Furthermore, the polymer (A) stored in the solution used in the polymerization in the same state after polymerization may be used as a component of the composition (D1) together with the solution. Alternatively, the polymer (A) used in the polymerization and stored in a solution adjusted to a pH of 5 or more may be used as a component of the composition (D1) together with the solution. Alternatively, the solution used in the polymerization may be removed and the polymer (A) may be used as a component of the composition (D1).

[0069] <Halogen Atoms> The composition (D1) according to the embodiment of the present invention contains halogen atoms, and the content of the halogen atoms is 0.7 ppm by mass or more and 1300 ppm by mass or less. The halogen atoms may or may not be contained in the polymer (A). The halogen atoms not contained in the polymer (A) may be in the form of an organic compound or an inorganic compound. When the composition (D1) contains halogen atoms, the hydration rate of the hydraulic composition can be easily controlled.

[0070] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. From the viewpoint of availability of raw materials, the halogen atom is preferably a chlorine atom.

[0071] The content of halogen atoms in composition (D1) is preferably 0.8 ppm by mass or more and 1000 ppm by mass or less, from the viewpoint of suppressing deterioration in fluidity over time. Note that the halogen atom content in this specification is a value obtained by combustion ion chromatography measurement, and the detailed measurement method can be according to the method described in the Examples.

[0072] <Compound (B)> From the viewpoint of further suppressing a decrease in fluidity over time, the composition (D1) according to the embodiment of the present invention preferably contains a compound (B) represented by the following general formula (III).

[0073]

[0074] In general formula (III), Y １ and Y ２ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. １ and Y ２ is preferably a chlorine atom.

[0075] h and i are each independently an integer of 1 to 4. From the viewpoint of ease of production, h and i are preferably 1 or 2, and more preferably 1.

[0076] When the composition (D1) contains the compound (B), the content of the compound (B) in the composition (D1) is preferably 0.01 to 5 mass%, more preferably 0.02 to 4 mass%, and even more preferably 0.05 to 3 mass%, from the viewpoint of efficiently obtaining the effects of the present invention.

[0077] <Polymer (C)> The composition (D1) of the present invention may contain a polymer (C) represented by the following general formula (V): When the composition (D1) contains the polymer (C), air is incorporated into the hydraulic composition to which the composition (D1) has been added, thereby further improving the fluidity of the hydraulic composition.

[0078]

[0079] In general formula (V), R ３１ and R ３２ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms.

[0080] From the viewpoint of ease of manufacturing, R ３１ and R ３２ is preferably a hydrogen atom, a methyl group, or an acetyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0081] R ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３３ is preferably a hydrogen atom, a methyl group, or an acetoxy group, more preferably a hydrogen atom or an acetoxy group, and even more preferably a hydrogen atom.

[0082] R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. From the viewpoint of ease of production and polymerizability, R ３４ , R ３５ , R ３６ , R ３７ , R３８ , R ３９ , R ４０ , and R ４１ are each independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0083] R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ Examples of the ring structure formed by bonding together include a single ring such as a cyclopropane ring, a cyclopentane ring, or a cyclohexane ring; a condensed ring such as a norbornane ring; a tetrahydrofuran ring, a pyrrolidine ring, or a tetrahydrothiophene ring.

[0084] R Ｃ and R Ｄ R each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ and R Ｄ The alkylene group having 2 to 6 carbon atoms represented by is the same as the above-mentioned R Ａ and R Ｂ The same groups as those exemplified as the "alkylene group having 2 to 6 carbon atoms" represented by the formula:

[0085] From the viewpoint of availability and reactivity, R Ｃ and R Ｄ is preferably an ethylene group, a propylene group, or a butylene group, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group.

[0086] A plurality of oxyalkylene-R Ｃ O- may be the same or different from each other. Ｄ The O- may be the same or different.

[0087] q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.

[0088] From the viewpoint of polymerizability, q and r are preferably 0. From the viewpoint of further improving the fluidity of the hydraulic composition and further suppressing a decrease in fluidity over time, q and r are preferably the same number. From the viewpoint of polymerizability, s and t are preferably integers of 10 to 50, more preferably integers of 10 to 40, and even more preferably integers of 15 to 30.

[0089] In one embodiment of the present invention, R ３３ is a hydrogen atom, and R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ are each independently a hydrogen atom or a methyl group. ３４ , R ３５ , R ３６ , and R ３７ is preferably a hydrogen atom, and q and r are preferably 0.

[0090] When the composition (D1) contains the polymer (C) represented by the general formula (V), there is no particular limitation on the content as long as sufficient fluidity is exhibited, but from the viewpoint of the strength of the cured product of the hydraulic composition, the content of the polymer (C) is preferably 0.01 to 50 mass%, more preferably 0.02 to 20 mass%, and even more preferably 0.02 to 10 mass%.

[0091] <Weight Average Molecular Weight of Polymer (C)> The weight average molecular weight of the polymer (C) is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and even more preferably 1,800 to 30,000, from the viewpoints of improving the fluidity of the hydraulic composition and suppressing a decrease in fluidity over time.

[0092] <Other Components> The first composition according to an embodiment of the present invention may contain, as necessary, an antifoaming agent, an air-enhancing agent, a cement dispersant, a strengthening improver, a hardening retarder, a hardening accelerator, a material separation reducer, a hydraulic powder, a non-hydraulic powder, an aggregate, water, an alcohol-based solvent such as methyl alcohol or ethyl alcohol, a hydrocarbon-based solvent such as toluene or n-hexane, an ester-based solvent such as ethyl acetate, a ketone-based solvent such as acetone or methyl ethyl ketone, an ether-based solvent such as tetrahydrofuran, or the like.

[0093] <Solids content concentration of composition (D1)> From the viewpoint of efficiently obtaining the effects of the present invention, the solids content concentration of composition (D1) is preferably 0.5 to 80 mass%, more preferably 1 to 50 mass%, and even more preferably 3 to 40 mass%.

[0094] <Method for producing composition (D1)> The composition (D1) according to the embodiment of the present invention may be produced by producing the above-mentioned polymer (A) and then mixing the polymer (A), a compound containing a halogen atom, and other components to produce the composition (D1). Alternatively, when producing the polymer (A), a compound containing a halogen atom and other components may be mixed with components from which structural units constituting the polymer (A) are derived, followed by polymerization, and the resulting reaction solution may be used as the composition (D1). From the viewpoint of ease of production and efficiently achieving the effects of the present invention, it is preferred that when producing the polymer (A), a compound containing a halogen atom and other components may be mixed with components from which structural units constituting the polymer (A) are derived, followed by polymerization, and the resulting reaction solution be used as the composition (D1). In this case, the method for producing the composition (D1) includes a step of obtaining the polymer (A) by heating a mixed solution containing an unsaturated polyalkylene glycol monomer, a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, and a compound (B-1) represented by the following general formula (VI), and it is more preferable that the amount of halogen atoms in the mixed solution is 0.7 ppm by mass or more and 1,300 ppm by mass or less.

[0095] The unsaturated polyalkylene glycol monomer used in the production of the composition (D1) includes the compound (C) represented by the above general formula (V).

[0096] Examples of the polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, which is used to produce the composition (D1), include the polymerizable monomers having a polymerizable unsaturated group and an acid group in one molecule described in the above <Structural unit (b)>.

[0097] In general formula (VI), Y ５ and Y ６ each independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. ５ and Y ６ is preferably a chlorine atom.

[0098] l and m each independently represent an integer of 1 to 4. From the viewpoint of ease of production, l and m are preferably 1 or 2, and more preferably 1.

[0099] The amount of halogen atoms in the mixed solution containing the unsaturated polyalkylene glycol monomer, the polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, and the compound (B-1) represented by the general formula (VI) is more preferably 1 to 1,100 ppm by mass, even more preferably 5 to 1,000 ppm by mass, more preferably 10 to 800 ppm by mass, and still more preferably 15 to 500 ppm by mass, from the viewpoint of further improving the fluidity of the hydraulic composition and further suppressing a decrease in fluidity over time.

[0100] The polymerization method may be the polymerization method described above in <Production method of polymer (A)>, and the preferred embodiments are also the same.

[0101] [Second composition (D2)] The second composition according to an embodiment of the present invention comprises a polymer (C) represented by the following general formula (V) and halogen atoms, and the content of the halogen atoms is 0.7 ppm by mass or more and 1300 ppm by mass or less. In this specification, the second composition (D2) may also be referred to as "composition (D2)".

[0102]

[0103] The composition (D2) according to the embodiment of the present invention contains a polymer (C) having a specific structure and a specific amount of halogen atoms, and thereby can improve the fluidity of the hydraulic composition and suppress a decrease in fluidity over time.

[0104] In the above general formula (V), R ３１ ~R ４１ , R Ｃ , R Ｄ , q, r, s, and t are the same as those in the <Polymer (C)> in the above [First composition (D1)], and preferred embodiments are also the same. In addition, the preferred weight average molecular weight of the polymer (C) contained in the composition (D2) is also the same as those in the <Polymer (C)> in the above [First composition (D1)].

[0105] The content of the polymer (C) in the composition (D2) is preferably 0.01 to 30 mass%, more preferably 0.02 to 20 mass%, and even more preferably 0.05 to 10 mass%, from the viewpoint of efficiently obtaining the effects of the present invention.

[0106] Composition (D2) according to an embodiment of the present invention contains halogen atoms, and the content of the halogen atoms is 0.7 ppm by mass or more and 1300 ppm by mass or less. The inclusion of halogen atoms in composition (D2) makes it easier to control the hydration rate of the hydraulic composition. Examples of halogen atoms include those exemplified in <Halogen Atoms> for [Composition (D1)] above, and preferred embodiments are also similar. From the viewpoint of suppressing a decrease in fluidity over time, the content of halogen atoms in composition (D2) is preferably 1 ppm by mass or more and 1100 ppm by mass or less, more preferably 5 ppm by mass or more and 1000 ppm by mass or less, even more preferably 10 ppm by mass or more and 800 ppm by mass or less, and even more preferably 15 ppm by mass or more and 500 ppm by mass or less.

[0107] The composition (D2) may contain the above-mentioned compound (B), and may also contain components other than the polymer (C) and halogen atoms. Examples of the components other than the polymer (C) and halogen atoms include antifoaming agents, air-enhancing agents, cement dispersants, strengthening improvers, set retarders, set accelerators, material separation reducers, hydraulic powders, non-hydraulic powders, aggregates, water, alcohol-based solvents such as methyl alcohol and ethyl alcohol, hydrocarbon-based solvents such as toluene and n-hexane, ester-based solvents such as ethyl acetate, ketone-based solvents such as acetone and methyl ethyl ketone, and ether-based solvents such as tetrahydrofuran.

[0108] From the viewpoint of efficiently achieving the effects of the present invention, the solids concentration of the composition (D2) is preferably 0.5 to 80 mass %, more preferably 1 to 50 mass %, and even more preferably 3 to 40 mass %.

[0109] The composition (D2) according to the embodiment of the present invention may be produced by producing the above-mentioned polymer (C) and then mixing the polymer (C), a compound containing a halogen atom, and other components, to produce the composition (D2). Alternatively, when producing the polymer (C), a compound containing a halogen atom and other components may be mixed with components from which structural units constituting the polymer (C) are derived, followed by polymerization, and the resulting reaction solution may be used as the composition (D2).

[0110] [Cement admixture] Composition (D1) and composition (D2) according to the present embodiment (hereinafter also referred to simply as "composition") can be suitably used as components of a cement admixture, and the cement admixture according to the present embodiment includes the composition according to the present embodiment. The cement admixture according to the present embodiment can improve the fluidity of a hydraulic composition and suppress a decrease in fluidity over time.

[0111] The cement admixture may contain other components in addition to the composition of the present invention, as long as the effects of the present invention are not impaired. Examples of other components include antifoaming agents, air-enhancing agents, cement dispersants, strengthening improvers, set retarders, set accelerators, material separation reducers, hydraulic powders, non-hydraulic powders, aggregates, water, alcoholic solvents such as methyl alcohol and ethyl alcohol, hydrocarbon solvents such as toluene and n-hexane, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as tetrahydrofuran.

[0112] Examples of the defoaming agent include oxyalkylene-based defoaming agents, silicone-based defoaming agents, and aliphatic amine-based defoaming agents. Preferred oxyalkylene-based defoaming agents are polyoxyalkylene glycol alkyl ethers, preferred silicone-based defoaming agents are dimethylpolysiloxane, and preferred aliphatic amine-based defoaming agents are alkyldimethylamines and their salts. One or more types of defoaming agents may be used in combination.

[0113] Examples of the air-entraining agent include resin soaps, saturated or unsaturated fatty acids, modified rosin acids, alkylaryl sulfonates, and polyoxyalkylene alkyl ether sulfates. Among these, modified rosin acids and alkylaryl sulfonates are preferred. One or more types of air-entraining agents may be used in combination.

[0114] Examples of cement dispersants include polyalkylaryl sulfonates such as naphthalene sulfonic acid formaldehyde condensates, melamine formalin resin sulfonates such as melamine sulfonic acid formaldehyde condensates, lignin sulfonates, polycarboxylic acid dispersants, phosphate dispersants containing phosphate groups, etc. One or more types of cement dispersants may be used in combination.

[0115] Examples of the strength improver include alkanolamines, such as triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc. One or more types of strength improvers may be used in combination.

[0116] Examples of the setting retarder include oxycarboxylic acids (salts) such as gluconic acid (salt), citric acid (salt), and tartaric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, and phosphonic acids such as aminotri(methylenephosphonic acid). One or more setting retarders may be used in combination.

[0117] Examples of the hardening accelerator include soluble calcium salts such as calcium chloride and calcium nitrite, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfates, formic acid and calcium formate, etc. One or more hardening accelerators may be used in combination.

[0118] Examples of the material separation reducing agent include various thickeners such as nonionic cellulose ethers. One or more types of material separation reducing agents may be used in combination.

[0119] Hydraulic powder refers to a powder that hardens when it comes into contact with water. Examples of hydraulic powders include Portland cement, calcium silicate, calcium aluminate, calcium fluoroaluminate, calcium sulfoaluminate, calcium aluminoferrite, calcium phosphate, gypsum hemihydrate, gypsum anhydrite, and self-hardening quicklime powder. One or more hydraulic powders may be used in combination depending on the desired physical properties of concrete.

[0120] Non-hydraulic powder refers to a powder that does not harden by itself even when it comes into contact with water, and also includes powders whose components are eluted in an alkaline or acidic atmosphere, or in a high-pressure steam atmosphere, and react with other eluted components to form a product. Examples of non-hydraulic powders include calcium hydroxide powder, gypsum dihydrate powder, calcium carbonate powder, silica powder, clay powder, granulated blast furnace slag, fly ash, and silica fume. One or more non-hydraulic powders may be used in combination depending on the desired physical properties of concrete.

[0121] Any aggregate may be used as the aggregate, such as fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.). Examples of such aggregates include gravel, crushed stone, granulated slag, and recycled aggregate. Other examples of such aggregates include refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia. One or more types of aggregate may be used in combination depending on the desired physical properties of the concrete.

[0122] The content of the composition in the cement admixture can be adjusted appropriately depending on the purpose. From the viewpoint of imparting fluidity to cement, the content of the composition in the cement admixture is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and may be 100% by mass.

[0123] From the viewpoint of efficiently obtaining the effects of the present invention, the solid content concentration of the cement admixture is preferably 10 to 100 mass %, more preferably 20 to 100 mass %, and even more preferably 30 to 100 mass %.

[0124] [Hydraulic Composition] The hydraulic composition according to this embodiment includes the composition according to this embodiment. When the hydraulic composition includes the composition, fluidity is improved and a decrease in fluidity over time can be suppressed. The hydraulic composition refers to a cement paste, a mortar composition, a concrete composition, or the like. The hydraulic composition according to this embodiment may be an unhardened product before hardening, a partially hardened semi-hardened product, or a hardened product. The hydraulic composition includes a solidifying agent such as cement, aggregate such as sand, gravel, or stone, water, etc., and may optionally include cement admixtures such as antifoaming agents, air-enhancing agents, and cement dispersants, strengthening improvers, hardening retarders, hardening accelerators, material separation reducers, hydraulic powders, non-hydraulic powders, alcohol solvents such as methyl alcohol and ethyl alcohol, hydrocarbon solvents such as toluene and n-hexane, ester solvents such as ethyl acetate, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as tetrahydrofuran, etc.

[0125] The contents of the composition and cement admixture in the hydraulic composition can be adjusted appropriately depending on the purpose. The content of the composition in the hydraulic composition is preferably 0.001 to 10 mass%, more preferably 0.001 to 5 mass%, and even more preferably 0.001 to 3 mass%. The content of the cement admixture in the hydraulic composition is preferably 0.001 to 20 mass%, more preferably 0.001 to 10 mass%, and even more preferably 0.001 to 5 mass%.

[0126] In addition to being used as a cement admixture, the composition of the present invention can be used in a wide range of applications, such as an aqueous slurry dispersant for inorganic pigments, a scale inhibitor, a detergent builder, a deinking agent for recycled waste paper, a chelating agent, a dispersant for various dyes, a dispersant for agricultural chemicals, a cotton scouring cleaner, a dispersant for coal, a thickener, a flocculant, and non-aqueous applications, and can exhibit excellent performance.

[0127] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0128] [Measurement and Evaluation Methods] Various physical properties were measured or evaluated by the following methods.

[0129] <Weight-average molecular weight> The weight-average molecular weight of the polymer in the composition obtained in the following examples and comparative examples was measured by gel permeation chromatography (GPC) under the following conditions and calculated in terms of standard polystyrene. Apparatus: "HLC-8320GPC" manufactured by Tosoh Corporation Eluent: tetrahydrofuran Column: two "TSKgel SuperMultiporeHZ-M" (inner diameter 4.6 mm, effective length 15 cm) and two "SuperH-RC" (inner diameter 4.6 mm, effective length 15 cm) manufactured by Tosoh Corporation connected in series Column temperature: 40°C Detector: RI Flow rate: 0.35 mL / min

[0130] <Halogen Atom Content> The halogen atom content (chlorine atom content) in the compositions obtained in the following examples and comparative examples was measured using the following equipment and ion chromatograph: Automatic sample combustion equipment: "AQF-2100H" manufactured by Nitto Seiko Analytech Co., Ltd. Ion chromatograph system: "ICS-2100" manufactured by Nippon Dionec Co., Ltd. Detector: Electrical conductivity detector

[0131] <Mini-Slump Test (Evaluation of Fluidity)> To evaluate the fluidity of the cement paste containing the composition, a mini-slump test was performed using the following method. 0.77 g of an aqueous composition solution prepared by adding distilled water so that the concentrations of the polymers (A-1) to (A-8) in the composition were 10% by mass, 37.73 g of distilled water, and 110 g of ordinary Portland cement (manufactured by Taiheiyo Cement Corporation) were mixed using a mixer to produce a cement paste. The cement paste was poured into a mini-slump cone described in Reference 1 on a stainless steel plate, and immediately after the cement paste injection (0 minutes) and 90 minutes after the cement paste injection (90 minutes), the mini-slump cone was pulled up under the conditions described in Reference 1, and the vertical and horizontal spreads of the cement paste (length and width) were measured, and the average value was used as the slump flow value. Using the obtained slump flow value, the slump flow retention rate was calculated using the following formula. Slump flow retention rate = [(slump flow value 90 minutes after cement paste injection (90 minutes)) / (slump flow value immediately after cement paste injection (0 minutes)] × 100 (%) A higher slump flow retention rate means that the decrease in fluidity over time is more suppressed. A slump flow retention rate of 75% or more was evaluated as G (Good), and a slump flow retention rate of less than 75% was evaluated as B (Bad).

[0132] Reference 1: Cement. Concrete. and Aggregates. CCAGDP, Vol. 2, No. 2, Winter 1980, pp95-102.

[0133] [Production Example 1] 2-Hydroxymethyl-3-propen-1-ol was reacted with ethylene oxide by a known method to obtain a compound (1) represented by the following formula (1).

[0134]

[0135] Example 1 A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 7.00 g of a mixture of compound (2) (manufactured by Kuraray Co., Ltd.) represented by the following formula (2) and compound (1) (number of moles of compound (1): 3.78 mmol, content of compound (2): 0.47 mg), and 4.99 g of distilled water. The amount of halogen atoms (chlorine atoms) contained in compound (2) was 38.1 ppm by mass in terms of the amount of chlorine atoms relative to compound (1). Subsequently, the internal temperature was raised to 60°C with stirring under a nitrogen stream, and 0.05 ml of a 30% by mass aqueous hydrogen peroxide solution (0.49 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added. An aqueous solution of 0.48 g (6.68 mmol) of acrylic acid dissolved in 3.09 g of distilled water and an aqueous solution of 20 mg of L-ascorbic acid (0.12 mmol, Tomifilm, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 2.76 g of distilled water were each added dropwise over 36 minutes, followed by reaction at 60°C for 1 hour. The resulting reaction mixture was cooled to obtain composition 1 containing polymer (A-1). The evaluation results of composition 1 are shown in Table 1.

[0136]

[0137] Example 2 A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 5.20 g of a mixture of compound (2) (manufactured by Kuraray Co., Ltd.) represented by the following formula (2) and compound (1) (molar number of compound (1): 2.81 mmol, content of compound (2): 18.86 mg), and 7.20 g of distilled water. The amount of halogen atoms (chlorine atoms) contained in compound (2) was 56.7% by mass in terms of chlorine atom weight relative to compound (1). Subsequently, the internal temperature was raised to 60°C with stirring under a nitrogen stream, and 0.015 ml of a 30% by mass aqueous hydrogen peroxide solution (0.146 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added. An aqueous solution prepared by dissolving 0.79 g (10.96 mmol) of acrylic acid in 1.20 g of distilled water and an aqueous solution prepared by dissolving 15 mg of L-ascorbic acid (0.085 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) in 1.2 g of distilled water were each added dropwise over 2 hours, followed by reaction at 60°C for 1 hour. The resulting reaction mixture was cooled to obtain composition 2 containing polymer (A-2). The evaluation results of composition 2 are shown in Table 1.

[0138] Example 3 The reaction was carried out in the same manner as in Example 2, except that the content of compound (2) in compound (1) was changed to 30.12 mg, to obtain composition 3 containing polymer (A-3). The evaluation results of composition 3 are shown in Table 1.

[0139] Example 4 A reactor equipped with a stirrer, a thermometer, and a dropping funnel was charged with 5.20 g of a mixture of sodium chloride and compound (1) (molar number of compound (1): 2.81 mmol, sodium chloride content: 17.94 mg) and 7.20 g of distilled water. The amount of halogen atoms (chlorine atoms) contained in the sodium chloride was 60.7% by mass in terms of chlorine atom weight relative to compound (1). Subsequently, the internal temperature was raised to 60°C with stirring under a nitrogen stream, and 0.015 ml of a 30% by mass aqueous hydrogen peroxide solution (0.146 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added. An aqueous solution of 0.79 g (10.96 mmol) of acrylic acid dissolved in 1.20 g of distilled water and an aqueous solution of 15 mg of L-ascorbic acid (0.085 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 1.2 g of distilled water were each added dropwise over 2 hours, followed by reaction at 60°C for 1 hour. The resulting reaction mixture was cooled to obtain composition 4 containing polymer (A-4). The evaluation results of composition 4 are shown in Table 1.

[0140] Example 5 The reaction was carried out in the same manner as in Example 2, except that 31.03 mg of sodium chloride was added to compound (1), to obtain composition 5 containing polymer (A-5). The evaluation results of composition 5 are shown in Table 1.

[0141] Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that only compound (1) was used instead of a mixture of compound (2) and compound (1), to obtain composition 6 containing polymer (A-6). The evaluation results of composition 6 are shown in Table 1.

[0142] [Comparative Example 2] A cement paste was produced in the same manner as in Example 1 and Comparative Example 1, except that the aqueous composition solution was not added, and a mini-slump test was carried out, the results of which are shown in Table 1. Note that, 90 minutes after the cement paste injection, the cement paste did not flow, and the slump flow value could not be measured.

[0143] Comparative Example 3 A composition 7 containing a polymer (A-7) was obtained by carrying out the reaction in the same manner as in Example 2, except that the content of compound (2) in compound (1) was changed to 100.26 mg. The evaluation results of composition 7 are shown in Table 1.

[0144] Comparative Example 4 A reaction was carried out in the same manner as in Example 4, except that the content of sodium chloride in compound (1) was changed to 92.90 mg, to obtain composition 8 containing polymer (A-8). The evaluation results of composition 8 are shown in Table 1.

[0145]

[0146] It is clear from Table 1 that the composition of the present invention improves the fluidity of hydraulic compositions and suppresses a decrease in fluidity over time. Therefore, the composition of the present invention can be suitably used in cement admixtures and hydraulic compositions.

Claims

1. A composition comprising: a polymer (A) containing a structural unit (a) represented by the following general formula (I) and a structural unit (b) represented by the following general formula (II); and halogen atoms, wherein the content of the halogen atoms is 0.7 ppm by mass or more and 1,300 ppm by mass or less. (In general formula (I), R １ and R ２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ may be bonded to each other to form a ring structure. Ａ and R Ｂ each independently represents an alkylene group having 2 to 6 carbon atoms. Ａ O- may be the same or different. Ｂ O- may be the same or different. o and p each independently represent 0 or 1, and m and n each independently represent an integer of 5 to 100. * represents a bond. (In general formula (II), R ２１ , R ２２ , and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a carboxy group, or an alkanoyloxy group having 2 to 6 carbon atoms linked together. X represents a carboxylate group, a phosphonate group, a sulfonate group, or a silicate group. M represents a hydrogen atom, an alkali metal atom, or ammonium. * represents a bond.

2. The composition of claim 1, wherein said halogen atom is a chlorine atom.

3. The composition according to claim 1 or 2, comprising from 0.7 ppm by mass to 1,000 ppm by mass of a compound (B) represented by the following general formula (III): (In general formula (III), Y １ and Y ２ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and each of h and i independently represents an integer of 1 to 4.

4. The composition according to any one of claims 1 to 3, wherein the polymer (A) contains 5 mol % or less of a structural unit (c) represented by the following general formula (IV) relative to the structural unit (a): (In general formula (IV), Y ３ and Y ４ each independently represents a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; j and k each independently represent an integer of 1 to 4; * represents a bond.

5. In the general formula (I), R ３ represents a hydrogen atom, R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , and R １１ The composition according to any one of claims 1 to 4, wherein each independently represents a hydrogen atom or a methyl group.

6. In the general formula (I), R ４ , R ５ , R ６ , and R ７ The composition according to any one of claims 1 to 5, wherein represents a hydrogen atom, and o and p are 0.

7. In the above general formula (I), R Ａ and R Ｂ The composition according to any one of claims 1 to 6, wherein each independently represents an ethylene group, a propylene group, or a butylene group.

8. The composition according to any one of claims 1 to 7, wherein the content of the halogen atoms is 0.8 ppm by mass or more and 1,000 ppm by mass or less.

9. A method for producing the composition according to any one of claims 1 to 8, comprising the step of obtaining the polymer (A) by heating a mixed solution containing an unsaturated polyalkylene glycol monomer, a polymerizable monomer having a polymerizable unsaturated group and an acid group in one molecule, and a compound (B-1) represented by the following general formula (VI), wherein the amount of halogen atoms in the mixed solution is 0.7 ppm by mass or more and 1,300 ppm by mass or less. (In general formula (VI), Y ５ and Y ６ each independently represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; and each of l and m independently represents an integer of 1 to 4.

10. A cement admixture comprising the composition according to any one of claims 1 to 8.

11. A hydraulic composition comprising the composition according to any one of claims 1 to 8.

12. A composition comprising a polymer (C) represented by the following general formula (V) and halogen atoms, the content of the halogen atoms being 0.7 ppm by mass or more and 1,300 ppm by mass or less: (In general formula (V), R ３１ and R ３２ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyl group having 2 to 6 carbon atoms. ３３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkanoyloxy group having 2 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ , R ４０ , and R ４１ may be bonded to each other to form a ring structure. Ｃ and R Ｄ each independently represents an alkylene group having 2 to 6 carbon atoms. Ｃ O- may be the same or different. Ｄ O- may be the same or different. q and r each independently represent 0 or 1, and s and t each independently represent an integer of 5 to 100.

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