JP2017186248A - Admixture composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an admixture composition which contains a shrinkage reducing agent capable of sufficiently exhibiting both shrinkage reducing performance and flowability of a cement composition, and a polycarboxylic acid-based water-reducing agent.SOLUTION: An admixture composition contains a shrinkage reducing agent for a hydraulic material and a polycarboxylic acid-based water-reducing agent, where the shrinkage reducing agent for the hydraulic material contains a predetermined compound.SELECTED DRAWING: None

Description

The present invention relates to an admixture composition. More specifically, the present invention relates to an admixture composition that can be suitably used for a cement composition or the like.

Hydraulic materials are widely used as cement compositions such as cement paste, mortar, and concrete because they give a cured product with excellent strength and durability. It is indispensable.
As hydraulic materials, admixtures other than cement, water, and aggregate are used mainly for the purpose of improving the quality of concrete and the like. In particular, in order to improve fluidity and workability, additives are generally used among admixtures. AE agent, water reducing agent, AE water reducing agent, high performance water reducing agent, fluidizing agent, high Various additives such as performance AE water reducing agent and shrinkage reducing agent are used. In addition, for the purpose of exhibiting more excellent performance, it has been studied to use a mixture of these additives.
For example, Patent Documents 1 to 6 disclose that a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent as a high-performance AE water reducing agent are used in combination.

Patent No. 4056809 Patent No. 4409309 JP 2002-293596 A JP 2007-79671 A JP 2008-230865 A JP 2001-247346 A

As described above, cement compositions containing a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent have been developed. However, when a conventional shrinkage reducing agent and a polycarboxylic acid-based water reducing agent are used in combination, There is room for improvement because it is not sufficient in terms of compatibility between the reducing property and the fluidity of the cement composition.

The present invention has been made in view of the above situation, and includes an admixture containing a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent capable of sufficiently exhibiting both shrinkage reduction properties and fluidity of a cement composition. An object is to provide a composition.

The inventor has conducted various studies on shrinkage reducing agents that can be used in combination with polycarboxylic acid-based water reducing agents. When a compound having a specific structure is used in combination with a polycarboxylic acid-based water reducing agent, the amount of these additives added is reduced. The inventors have found that both the shrinkage reduction property and the fluidity of the cement composition are excellent even in a small amount, and have conceived that the above-mentioned problems can be solved brilliantly and have reached the present invention.

（式（１）中、Ｒ^１〜Ｒ^３は、同一又は異なって、水素原子又はメチル基を表す。Ｒ^４Ｏは、同一又は異なって、炭素数２〜１８のオキシアルキレン基を表す。Ｒ^５は、水素原子又は炭素数１〜３０の炭化水素基を表す。ｐは、０〜５の数を表し、ｑは、０又は１の数である。ｎは、オキシアルキレン基の平均付加モル数を表し、７〜３００の数である。）で表される構造単位（Ｉ）と、下記式（２）；

（式（２）中、Ｒ^６〜Ｒ^８は、同一又は異なって、水素原子、メチル基又は−（ＣＨ_２）_ｍＣＯＯＺ’基を表す。ここで、ｍは、０〜２の整数であり、Ｚ’は、水素原子、金属原子、アンモニウム基、有機アミン基又は炭化水素基を表す。Ｚは、水素原子、金属原子、アンモニウム基又は有機アミン基を表す。）で表される構造単位（ＩＩ）とを有する重合体であって、
該重合体は、構造単位（Ｉ）の割合が、全構造単位１００質量％に対して、７０〜９７質量％であり、構造単位（ＩＩ）の割合が、全構造単位１００モル％に対して、１０〜５９モル％であり、重量平均分子量が、４０００〜３２０００である重合体
（ＩＩ）：
下記式（３）；
［Ｖ−（ＯＡ^１）_ｆ−］_ｋＹ［−（Ｂ^１Ｏ）_ｇ−Ｗ］_ｌ （３）
（式（３）中、Ｖ、Ｗは、同一又は異なって、水素原子又は炭素原子数１〜３０の炭化水素基を表す。ＯＡ^１、Ｂ^１Ｏは、同一又は異なって、炭素数２〜１８のオキシアルキレン基を表す。ｆ、ｇは、それぞれ、ＯＡ^１、Ｂ^１Ｏの平均付加モル数を表し、ｆ、ｇは、同一又は異なって、０〜２０００であり、ｆ＋ｇ＝１〜２０００である。Ｙは活性水素を有する化合物の残基を表す。ｋ、ｌは、同一又は異なって、０〜６である。ただし、ｋ＋ｌは１以上である。）で表されるポリエーテル化合物にエチレン性不飽和単量体をグラフト重合してなる重合体であって、該エチレン性不飽和単量体は不飽和カルボン酸系単量体を含み、該重合体は、不飽和カルボン酸系単量体由来の構造単位の割合が、全構造単位１００質量％に対して、０．１〜１２質量％であり、該ポリエーテル化合物の重量平均分子量が、１５００〜５００００である重合体
（ＩＩＩ）：
エチレン性不飽和単量体成分由来の高分子鎖（Ａ）と（ポリ）アルキレングリコール鎖（Ｂ）の末端とが結合部位（Ｘ）を介して結合した構造を有する共重合体であって、該エチレン性不飽和単量体は、不飽和アニオン系単量体を含み、該共重合体は、不飽和アニオン系単量体由来の構造単位の割合が、（ポリ）アルキレングリコール鎖１モルに対して１〜３０モルであり、（ポリ）アルキレングリコール鎖を形成する（ポリ）アルキレングリコールの重量平均分子量が、１５００〜５００００である（ポリ）アルキレングリコール系ブロック共重合体
（ＩＶ）：
直鎖状又は分岐状ポリアルキレングリコール鎖の少なくとも２つの末端に、金属、金属化合物及び金属イオンの少なくとも１つに対して吸着能を示す有機残基が結合したポリアルキレングリコール化合物であって、該ポリアルキレングリコール化合物は、ポリアルキレングリコール鎖を形成するポリアルキレングリコールの重量平均分子量が、１５００〜５００００であり、該有機残基は、カルボニル基、水酸基、アミノ基、チオール基、リン酸基、亜リン酸基及びシラン基からなる群より選択される少なくとも１つの官能基を有するポリアルキレングリコール化合物
（Ｖ）：
酸基含有側鎖を有するポリアミン化合物であって、該ポリアミン化合物は、未置換ポリアミン化合物由来の構造単位と不飽和カルボン酸系単量体由来の構造単位とを有し、該不飽和カルボン酸系単量体由来の構造単位の割合が、全構造単位１００モル％に対して、２５〜９９モル％である酸基含有側鎖を有するポリアミン化合物
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。 That is, the present invention is an admixture composition comprising a shrinkage reducing agent for hydraulic material and a polycarboxylic acid-based water reducing agent, wherein the shrinkage reducing agent for hydraulic material comprises the following (I) to (V): An admixture composition comprising at least one compound selected from the group.
(I):
Following formula (1);

(In Formula (1), R < ¹ > -R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R < ⁴ > O is the same or different and represents a C2-C18 oxyalkylene group. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, p represents a number of 0 to 5, q represents a number of 0 or 1. n represents an average addition mole of an oxyalkylene group. A structural unit (I) represented by the following formula (2):

(In the formula ^(2), R 6 ~R ⁸ are the same or different, a hydrogen atom, a methyl group or a _-. (Representing _CH 2) m COOZ 'group wherein, m is an integer from 0 to 2 , Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group, and Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). II)
In the polymer, the proportion of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of all the structural units, and the proportion of the structural unit (II) is 100% by mol with respect to all the structural units. 10 to 59 mol%, and the polymer (II) having a weight average molecular weight of 4000 to 32000:
Following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In Formula (3), V and W are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. OA ¹ and B ¹ O are the same or different and have 2 to 2 carbon atoms. 18 represents an oxyalkylene group, and f and g represent the average number of added moles of OA ¹ and B ¹ O, respectively, and f and g are the same or different and are 0 to 2000, and f + g = 1 to 2000. Y represents a residue of a compound having active hydrogen, and k and l are the same or different and are 0 to 6. However, k + 1 is 1 or more. A polymer obtained by graft polymerization of an ethylenically unsaturated monomer, the ethylenically unsaturated monomer containing an unsaturated carboxylic acid monomer, and the polymer comprising an unsaturated carboxylic acid monomer The proportion of the structural unit derived from the monomer is 0 with respect to 100% by mass of all the structural units. 1 to 12 wt%, weight average molecular weight of the polyether compound is a 1,500 to 50,000 polymer (III):
A copolymer having a structure in which a polymer chain derived from an ethylenically unsaturated monomer component (A) and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X), The ethylenically unsaturated monomer includes an unsaturated anionic monomer, and the copolymer has a ratio of structural units derived from the unsaturated anionic monomer to 1 mol of the (poly) alkylene glycol chain. The (poly) alkylene glycol block copolymer (IV) having a weight average molecular weight of 1 to 30 moles and the weight average molecular weight of the (poly) alkylene glycol forming the (poly) alkylene glycol chain is 1500 to 50000:
A polyalkylene glycol compound in which an organic residue capable of adsorbing at least one of a metal, a metal compound, and a metal ion is bonded to at least two ends of a linear or branched polyalkylene glycol chain, In the polyalkylene glycol compound, the polyalkylene glycol forming the polyalkylene glycol chain has a weight average molecular weight of 1500 to 50000, and the organic residue includes a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphate group, Polyalkylene glycol compound (V) having at least one functional group selected from the group consisting of a phosphate group and a silane group:
A polyamine compound having an acid group-containing side chain, the polyamine compound having a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid monomer, the unsaturated carboxylic acid type The polyamine compound having an acid group-containing side chain in which the proportion of the structural unit derived from the monomer is 25 to 99 mol% with respect to 100 mol% of all the structural units is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

(Shrinkage reducing agent for hydraulic materials)
The shrinkage reducing agent for hydraulic material contained in the admixture composition of the present invention contains at least one compound selected from the group consisting of the above (I) to (V). The present invention uses a shrinkage reducing agent having such a specific structure in combination with a polycarboxylic acid-based water reducing agent, which will be described later, to reduce shrinkage compared to a combination of an existing shrinkage reducing agent and a polycarboxylic acid-based water reducing agent. And the fluidity of the cement composition has been found to be improved.
In the following, details of each of the compounds (I) to (V) will be described.

<First Form: Compound (I)>
The compound of the above (I) is represented by the following formula (1);

(In Formula (1), R < ¹ > -R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R < ⁴ > O is the same or different and represents a C2-C18 oxyalkylene group. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, p represents a number of 0 to 5, q represents a number of 0 or 1. n represents an average addition mole of an oxyalkylene group. A structural unit (I) represented by the following formula (2):

(In the formula ^(2), R 6 ~R ⁸ are the same or different, a hydrogen atom, a methyl group or a _-. (Representing _CH 2) m COOZ 'group wherein, m is an integer from 0 to 2 , Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group, and Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). II).
The polymer (I) (hereinafter also referred to as polymer (I)) is composed of the structural unit (I) represented by the above formula (1) and the structural unit (II) represented by the formula (2). Each may contain 1 type, and may contain 2 or more types.

In the above formula (1), R ^{1 to} R ³ are the same or different and represent a hydrogen atom or a methyl group, but at least one of R ¹ and R ² is preferably a hydrogen atom.

The oxyalkylene group represented by — (R ⁴ O) — in the above formula (1) is an oxyalkylene group having 2 to 18 carbon atoms, and when two or more oxyalkylene groups are present, random addition, Any addition form such as block addition or alternate addition may be used.
The oxyalkylene group represented by — (R ⁴ O) — is preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 4 carbon atoms.
These oxyalkylene groups are alkylene oxide adducts, and examples of such alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferred are ethylene oxide, propylene oxide and butylene oxide, and still more preferred are ethylene oxide and propylene oxide.

The formula in ^{(1) - (R 4 O} ) - oxyalkylene group represented by, if those containing oxyethylene group ethylene oxide added, 50 to 100 oxyethylene groups in 100 mole% the total oxyalkylene groups It is preferable to contain mol%. By containing oxyethylene groups in such a ratio, it is possible to suppress the increase in air entrainment, to facilitate the adjustment of the air amount, and to suppress the decrease in strength and freeze-thaw resistance. it can. More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%, Especially preferably, it is 80-100 mol%, Most preferably, it is 90-100 mol%.

R ⁵ in the above formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. More preferably, it is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. And most preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
Hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl and heptyl groups. Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isooctyl group, 2,3,5-trimethylhexyl group, 4-ethyl-5-methyloctyl group and 2-ethylhexyl group, tetradecyl group, octadecyl group, Linear or branched alkyl group such as icosyl group; cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl group, benzyl group, phenethyl group, o-, m- or p -Tolyl group, 2,3- or 2,4-xylyl group, Shichiru group, a naphthyl group, anthryl group, phenanthryl group, a biphenylyl group, a benzhydryl group, and aryl groups such as trityl group and pyrenyl group. Among these, a linear, branched or cyclic alkyl group is preferable.

In the above formula (1), p represents a number of 0 to 5, and q represents a number of 0 or 1, but a preferable combination of p and q is a combination in which p is 1 or 2 and q is 0, or p Is a combination of 0 and q = 1.

In the above formula (1), n represents the average number of added moles of the oxyalkylene group and is a number of 7 to 300. When the average number of added moles exceeds 300, air entrainment becomes high and it becomes difficult to adjust the amount of air, and there is a risk that strength and freeze-thaw resistance may be reduced. The average added mole number of the oxyalkylene group is preferably 7 to 150. More preferably, it is 7-100, More preferably, it is 7-80, Especially preferably, it is 7-50, Most preferably, it is 7-30.

The monomer that forms the structural unit (I) represented by the above formula (1) can be obtained by adding an alkylene oxide in an amount of a predetermined number of repetitions to an unsaturated alcohol and / or an unsaturated carboxylic acid. Can do. Moreover, ester reaction of alcohol and unsaturated carboxylic acid obtained by adding the alkylene oxide of the quantity which becomes a predetermined repeating number to alcohol and phenols which have a C1-C30 hydrocarbon group, and / or It can also be obtained by a transesterification reaction with an unsaturated carboxylic acid ester.

Examples of the unsaturated alcohol include vinyl alcohol, allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2 -Methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol and the like are preferable.
Moreover, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, etc. are suitable. Furthermore, the unsaturated carboxylic acid ester may be an alkyl ester of these unsaturated carboxylic acids.
Examples of the alcohols and phenols having a hydrocarbon group having 1 to 30 carbon atoms include alkyl alcohols such as methanol, ethanol and butanol; alcohols having an aryl group such as benzyl alcohol; phenols such as phenol and paramethylphenol; Among these, alcohols having 1 to 3 carbon atoms such as methanol, ethanol and butanol are preferable.
As the alkylene oxide, those described above can be used.

^R 6 to R ⁸ in the formula (2) may be the same or different and each represents a hydrogen atom, a methyl group or _- represents a _(CH 2) m COOZ 'group.
In the — (CH ₂ ) _m COOZ ′ group, Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Here, lithium, sodium, potassium, etc. are mentioned as a monovalent metal. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like. Z ′ is a divalent metal in which any two or more of R ^{6 to} R ⁸ are — (CH ₂ ) _m COOZ ′ groups, and two of them —COO— are anhydrides. Or when any one of R ^{6 to} R ⁸ — (CH ₂ ) _m COOZ ′ group and COOZ is in the form of an anhydride.

When Z ′ is an organic amine group, the organic amine group includes primary amines such as methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine. Groups derived from amines; groups derived from secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dicyclohexylamine, dibenzylamine and diphenylamine; Groups derived from tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tricyclohexylamine, tribenzylamine and triphenylamine; and ethanolamine, diethano Examples include groups derived from alkanolamines such as allamine and triethanolamine. Among these, alkanolamine groups such as ethanolamine group, diethanolamine group, triethanolamine group, and triethylamine group are preferable.
When Z ′ is a hydrocarbon group, the hydrocarbon group preferably has 1 to 30 carbon atoms. More preferably, it is a C1-C20 thing, More preferably, it is a C1-C12 thing. Examples of the hydrocarbon group having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, Linear or branched alkyl groups such as undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl, tetradecyl, octadecyl, icosyl; cyclopropyl, cyclobutyl, cyclopentyl Cyclic alkyl groups such as cyclohexyl, cycloheptyl and cyclooctyl; phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthri , Biphenylyl, benzhydryl, and the like aryl groups such as trityl, and pyrenyl.

Among these, Z ′ is preferably a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group, and particularly preferably a hydrogen atom, sodium or calcium.
In the above formula (2), m is an integer of 0 to 2, preferably 0 or 1, and particularly preferably 0.

R ^{6 to} R ⁸ in the above formula (2) are the same or different and represent a hydrogen atom, a methyl group, or a — (CH ₂ ) _m COOZ ′ group, and in these, a — (CH ₂ ) _m COOZ ′ group R ⁷ is a — (CH ₂ ) _m COOZ ′ group, and R ⁶ and R ⁸ are preferably a hydrogen atom or a methyl group. Moreover, it is also a suitable form that all of R ^{6 to} R ⁸ are hydrogen atoms or methyl groups.

The monomer forming the structural unit (II) represented by the above formula (2) is an unsaturated carboxylic acid monomer, and the unsaturated carboxylic acid monomer is an unsaturated monocarboxylic acid monomer. Monomers and unsaturated dicarboxylic acid monomers are preferred. The unsaturated monocarboxylic acid monomer may be any monomer having one unsaturated group and one group capable of forming a carbanion in the molecule. For example, (meth) acrylic acid, crotonic acid , Tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid and the like; these monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts are preferred.
The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule. Maleic acid, itaconic acid, mesaconic acid, Citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides or half esters are preferred.

The compound of the first form includes a structural unit (I) represented by the above formula (1) and other structural units (III) other than the structural unit (II) represented by the above formula (2). You may have.
Other monomers forming the structural unit (III) include bifunctional (meth) acrylates such as hexanediol di (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,4 2-6 carbon atoms such as alkanediol mono (meth) acrylates such as butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate Hydroxyl group-containing (meth) acrylate compounds having a hydroxyalkyl group: alkoxy group-containing (meth) ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylethyl (meth) acrylate, methoxypropyl (meth) acrylate, etc. Acu Rate compounds; Amides of unsaturated monocarboxylic acid monomers as described above and amines having 1 to 30 carbon atoms, (meth) acrylamide, methyl (meth) acrylamide, (meth) acrylalkylamide, N -Unsaturated amides such as methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms, or addition mole number of these glycols of 2 to 500 ( Diesters with poly) alkylene glycols; half amides of maleamic acid and glycols having 2 to 18 carbon atoms or (poly) alkylene glycols having 2 to 500 addition moles of these glycols; hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylo Polyfunctional (meth) acrylates such as rupropanedi (meth) acrylate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy 2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) Unsaturated sulfonic acids such as acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, and styrenesulfonic acid, and monovalent metal salts and divalent metals thereof Salts, ammonium salts and organic amine salts; vinyl aromatics such as styrene, α-methylstyrene, bromostyrene, chlorostyrene, vinyltoluene and p-methylstyrene; α-olefins such as hexene, heptene and decene; methyl vinyl ether Alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; allyl esters such as allyl acetate; allyls such as allyl alcohol.

Dienes such as butadiene, isoprene, isobutylene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; unsaturated cyanates such as (meth) acrylonitrile and α-chloroacrylonitrile; vinyl acetate, propion Unsaturated esters such as vinyl acid; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutyl (meth) acrylate Unsaturated amines such as aminoethyl and vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxane aminopropyleneaminomaleamic acid, polydi Tylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl) -3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), siloxane derivatives such as polydimethylsiloxane-bis- (1-propyl-3-methacrylate).

In the polymer (I), the proportion of the structural unit (I) represented by the formula (1) is 70 to 97% by mass with respect to 100% by mass of all the structural units. The proportion of the structural unit (I) is preferably 85 to 97% by mass, more preferably 91 to 97% by mass.

In the polymer (I), the proportion of the structural unit (II) represented by the above formula (2) is 10 to 59 mol% with respect to 100 mol% of all structural units. If the ratio of structural unit (II) is the said range, the acid amount in polymer (I) will become a suitable range, and it will be excellent in shrinkage reduction performance. Preferably it is 20-55 mol% as a ratio of the said structural unit (II), More preferably, it is 25-50 mol%.

In the polymer (I), the proportion of the other structural unit (III) is preferably 0 to 20% by mass with respect to 100% by mass of all the structural units. More preferably, it is 0-15 mass%, More preferably, it is 0-10 mass%.
When polymer (I) has structural unit (III) essential, it is preferable that the mass ratio of structural unit (III) is 1 mass% or more.

In the polymer (I), the total proportion of the structural unit (II) represented by the formula (2) and the other structural unit (III) is 3 to 25% by mass with respect to 100% by mass of all the structural units. % Is preferred. More preferably, it is 5-20 mass%, More preferably, it is 5-15 mass%, Most preferably, it is 7-15 mass%.

The polymer (I) has a weight average molecular weight of 4000 to 32000. The weight average molecular weight of the polymer (I) is preferably 4500 to 32000, more preferably 5000 to 30000, and still more preferably 5000 to 28000. The weight average molecular weight of the polymer (I) can be measured by GPC under the conditions described in Examples described later.

The method for producing the polymer (I) is not particularly limited, but it is preferable to polymerize a monomer component that is a raw material of the polymer using a polymerization initiator.
The polymerization method of the monomer component is not particularly limited, and any polymerization method commonly used may be used, but the polymerization is preferably performed by a method such as polymerization in a solvent or bulk polymerization.
Polymerization in a solvent can be carried out either batchwise or continuously. The solvent used here is water; lower alcohols such as methyl alcohol, ethyl alcohol, 2-propanol; benzene, toluene, xylene, cyclohexane, Examples include aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone. In consideration of the solubility of the raw material monomer and the polymer to be obtained and the convenience during use of this polymer, it is preferable to use water and / or a lower alcohol having 1 to 4 carbon atoms, particularly water and / or Methyl alcohol, ethyl alcohol, 2-propanol and the like are preferable.
For other polymerization methods, JP-T-2007-529397 can be referred to.

The polymer thus obtained may be used as it is as a drying shrinkage reducing agent, but may be handled in the form of an aqueous solution containing no organic solvent. In such a case, the polymer is further monovalent. Metal and divalent metal hydroxides, chlorides, carbon salts and other inorganic substances; ammonia; neutralization with alkaline substances such as organic amines (preferably monohydric metal hydroxides such as sodium hydroxide and potassium hydroxide) Then, it may be used as a drying shrinkage reducing agent in the form of a polymer salt.
In addition, a compound having an amino group and an imino group as described in International Publication No. 2007/086507 and / or a compound having an amino group, an imino group, and an amide group are included in the polymer thus obtained. An alkylene oxide-modified water-soluble polymer having a structure in which an alkylene oxide is further added to a polymer skeleton bonded to each other by grafting and / or crosslinking may be contained.

<Second Form: Compound (II)>
The second form of the compound contained in the shrinkage reducing agent for hydraulic material is represented by the following formula (3);
^{_{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In Formula (3), V and W are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. OA ¹ and B ¹ O are the same or different and have 2 to 2 carbon atoms. 18 represents an oxyalkylene group, and f and g represent the average number of added moles of OA ¹ and B ¹ O, respectively, and f and g are the same or different and are 0 to 2000, and f + g = 1 to 2000. Y represents a residue of a compound having active hydrogen, and k and l are the same or different and are 0 to 6. However, k + 1 is 1 or more. A polymer obtained by graft polymerization of an ethylenically unsaturated monomer, wherein the ethylenically unsaturated monomer includes an unsaturated carboxylic acid monomer, and the polymer includes an unsaturated carboxylic acid monomer. The proportion of the structural unit derived from the monomer is 100% by mass of all the structural units. A 0.1 to 12 mass%, weight average molecular weight of the polyether compound is a polymer which is 1,500 to 50,000.

The graft polymer (hereinafter also referred to as polymer (II)) is obtained by graft polymerization of an ethylenically unsaturated monomer to a polyether compound. Such a graft polymer is composed of a polyether chain derived from a polyether compound and a graft chain in which an ethylenically unsaturated monomer is polymerized at a graft site of the polyether compound. In this invention, it has the effect | action (henceforth shrinkage reduction performance) which fully suppresses the progress of drying shrinkage of hardened | cured material by the effect | action of the said polyether chain | strand and the said graft chain | strand. In the preparation of the hydrophilic graft polymer, one type of ethylenically unsaturated monomer and one polyether compound may be used, or two or more types may be used in combination.

The ethylenically unsaturated monomer includes an unsaturated carboxylic acid monomer. The unsaturated carboxylic acid-based monomer is a monomer having at least one polymerizable unsaturated bond and a carboxyl group in the molecule, and an α, β-unsaturated dicarboxylic acid and / or an anhydride thereof. It is preferable to include. As a result, sudden thickening due to runaway polymerization reaction in the graft polymerization can be prevented.

In the polymer (II), the proportion of the structural unit derived from the unsaturated carboxylic acid monomer is 0.1 to 12% by mass with respect to 100% by mass of all the structural units. The proportion of the structural unit derived from the unsaturated carboxylic acid monomer is preferably 0.5 to 10% by mass, and more preferably 2 to 10% by mass.

As the α, β-unsaturated dicarboxylic acid and / or anhydride thereof, the same as the unsaturated dicarboxylic acid monomer in the polymer (I) described above can be used.

The content of the α, β-unsaturated dicarboxylic acid and / or anhydride thereof in the unsaturated carboxylic acid monomer is, for example, to prevent thickening by graft polymerization to a polyether compound at an appropriate rate. Is preferably 0.1 to 99.9% by weight. More preferably, it is 1-99 weight%, More preferably, it is 10-90 weight%, Most preferably, it is 20-80 weight%.

The unsaturated carboxylic acid monomer preferably contains an unsaturated carboxylic acid monomer other than the α, β-unsaturated dicarboxylic acid. As the unsaturated carboxylic acid monomer, those similar to the unsaturated monocarboxylic acid monomer in the first embodiment described above can be used.

In the present invention, one of the preferred embodiments of the unsaturated carboxylic acid monomer includes at least one selected from the group consisting of maleic acid, fumaric acid and maleic anhydride, and (meth) acrylic acid as essential. It is included as a component. In this embodiment, the weight ratio of (meth) acrylic acid to at least one compound selected from the group consisting of maleic acid, fumaric acid and maleic anhydride is, for example, 1/99 to 99/1. It is preferable. More preferably, it is 10 / 90-90 / 10, More preferably, it is 20 / 80-80 / 20, Most preferably, it is 30 / 70-70 / 30.

The ethylenically unsaturated monomer other than the unsaturated carboxylic acid-based monomer is not particularly limited, and examples thereof include ethylenically unsaturated carboxylic acid esters and other ethylenically unsaturated monomers. Examples of the ethylenically unsaturated carboxylic acid esters include maleic acid alkyl esters such as monomethyl maleate, dimethyl maleate, monoethyl maleate and diethyl maleate; monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, Alkyl esters of fumaric acid such as diethyl fumarate; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate; hydroxyethyl (meth) acrylate , Unsaturated carboxylic acid esters having a hydroxyl group such as hydroxyalkyl (meth) acrylate such as hydroxypropyl (meth) acrylate; (methoxy) polyethylene glycol (meth) acrylate, phenoxypo Ethylene glycol (meth) acrylate, naphthoxy polyethylene glycol (meth) acrylate, mono phenoxy polyethylene glycol maleates, polyalkylene glycol (meth) acrylates such as carbazole polyethylene glycol (meth) acrylate.

Examples of the ethylenically unsaturated monomer other than the ethylenically unsaturated carboxylic acid esters include those described below. Aromatic vinyl monomers such as styrene; vinyl monomers having an amide group such as (meth) acrylamide and (meth) acrylalkylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl monomers having a trialkyloxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane ; Vinyl monomers having a silicon atom such as γ- (methacryloyloxypropyl) trimethoxysilane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide Maleimide derivatives such as cyclohexyl maleimide.

Vinyl monomers having a nitrile group such as (meth) acrylonitrile; Vinyl monomers having an aldehyde group such as (meth) acrolein; Dialkylaminoethyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate Vinyl monomers having an amino group such as alkenyl; unsaturated ethers such as (methoxy) polyethylene glycol (meth) allyl ether and (methoxy) polyethylene glycol isopropenyl ether; 2-acrylamido-2-methylpropane sulfonic acid , (Meth) allylsulfonic acid, 2-sulfoethyl (meth) acrylate, vinylsulfonic acid, hydroxyallyloxypropanesulfonic acid, vinyl monomers having a sulfonic acid group such as styrenesulfonic acid; vinyl chloride, vinylidene chloride, Allyl chloride, ants Alcohol, vinyl monomers such as having other functional groups such as vinyl pyrrolidone, ethyl vinyl ether.

The amount of the ethylenically unsaturated monomer other than the unsaturated carboxylic acid monomer is preferably 0.1 to 20% by mass of the whole ethylenically unsaturated monomer. More preferably, it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%.

The amount of the ethylenically unsaturated monomer used is not particularly limited, but the polymer (II) is prepared by adding the ethylenically unsaturated monomer to the polyether compound. It is preferable that the unsaturated carboxylic acid monomer in the monomer is a graft polymer obtained by graft polymerization in an amount of 0.1 to 50% by weight based on the polyether compound. If it is less than 0.1% by weight, the hydrophilic graft polymer may hardly act on the hydraulic material and the shrinkage reduction performance may not be sufficient. There is a possibility that the curing delay of the hard material is increased, or the viscosity of the reaction mixture at the time of preparing the hydrophilic graft polymer becomes high, making it difficult to handle. More preferably, it is 0.5-30 weight%, More preferably, it is 1-20 weight%, Most preferably, it is 2-10 weight%.

In the polymer (II), the monomer component that is a raw material of the compound includes a polyether compound, an unsaturated carboxylic acid monomer, and an unsaturated carboxylic acid monomer that are raw materials of the graft polymer. It is a non-ethylenically unsaturated monomer other than a polyether compound, an unsaturated carboxylic acid monomer, and a molar ratio of an ethylenically unsaturated monomer other than an unsaturated carboxylic acid monomer. Is preferably 75-3 / 25-97 / 0-72. More preferably, it is 75-5 / 25-95 / 0-70, More preferably, it is 65-5 / 35-95 / 0-60, Especially preferably, it is 50-5 / 50-95 / 0 45, and most preferably 50 to 8/60 to 92/0 to 32.

The polyether compound in the polymer (II) is used as a raw material for preparing the graft polymer, and constitutes the polyether chain of the graft polymer. The balance between the hydrophilicity and the hydrophobicity of such a polyether compound greatly affects the balance between the hydrophilicity and the hydrophobicity of the hydrophilic graft polymer as it is. If the graft polymer is too hydrophilic, cement dispersibility may be improved, resulting in material separation and a decrease in alkali resistance of the cured product. If the hydrophobicity is too large, the amount of air in the hydraulic material may be excessively reduced to lower the fluidity and the like. Therefore, in the graft polymer of the second form, it is important to appropriately balance the hydrophilicity and hydrophobicity of the polyether compound. As an index representing such a balance between hydrophilicity and hydrophobicity, for example, there is HLB. To quantify HLB, for example, according to the Griffin formula described in Kitahara et al., “Surfactants—Physical Properties, Applications, Chemical Ecology—” (8th edition, August 10, 1991, issued by Kodansha). Can be calculated. As HLB of the said polyether compound, it is preferable that it is 8-20, for example. More preferably, it is 10-20, More preferably, it is 13-19.

In the polymer (II), the polyether compound is a compound represented by the formula (3). 1 type may be used for the compound represented by the said Formula (3), and 2 or more types may be used together.

In the above formula (3), V and W are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. V and W are preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. More preferably, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, still more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. And most preferably a hydrogen atom.
Hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl and heptyl groups. Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isooctyl group, 2,3,5-trimethylhexyl group, 4-ethyl-5-methyloctyl group and 2-ethylhexyl group, tetradecyl group, octadecyl group, Linear or branched alkyl group such as icosyl group; cyclic alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl group, benzyl group, phenethyl group, o-, m- or p -Tolyl group, 2,3- or 2,4-xylyl group, Shichiru group, a naphthyl group, anthryl group, phenanthryl group, a biphenylyl group, a benzhydryl group, and aryl groups such as trityl group and pyrenyl group. Among these, a linear, branched or cyclic alkyl group is preferable.

In the formula (3), the average added mole number means an average value of the number of moles of the repeating unit in 1 mole of the compound represented by the formula (3). The oxyalkylene group having 2 to 18 carbon atoms in the above formula (3) has a function of imparting appropriate hydrophobicity to the graft polymer.
F and g in the above formula (3) represent the average added mole number of OA ¹ and B ¹ O. f + g is preferably 25 or more from the viewpoint of improving the graft ratio of the graft polymer, improving the cement dispersibility, improving hydrophilicity, and the like. More preferably, it is 40 or more, More preferably, it is 50 or more. Moreover, it is preferable that it is 1000 or less, More preferably, it is 500 or less.

In the above formula (3), OA ¹ and B ¹ O are “same or different” and represent an oxyalkylene group having 2 to 18 carbon atoms, which is present in f or g in the polyalkylene glycol. It means that all oxyalkylene groups of OA ¹ or B ¹ O may be the same or different.
In the group represented by-(OA ¹ )-and-(B ¹ O)-in the above formula (3), the oxyalkylene group having 2 to 18 carbon atoms may be one type or two or more types. There may be. When there are two or more kinds, the repeating form of the oxyalkylene group may be random, block, alternating, or the like.
Further, in the groups represented by-(OA ¹ )-and-(B ¹ O)-in the above formula (3), the average addition of oxyethylene groups in the average addition mole number of oxyalkylene groups having 2 to 18 carbon atoms. The mole ratio is preferably 50% or more. More preferably, it is 60% or more, still more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more.

Y in the above formula (3) represents a residue of a compound having active hydrogen. Active hydrogen means hydrogen to which alkylene oxide can be added, and a residue of a compound having active hydrogen means a group having a structure obtained by removing active hydrogen from a compound having active hydrogen. Examples of the compound having active hydrogen include monohydric alcohols having 1 to 30 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and 2-ethylhexanol; ethylene glycol, propylene glycol and the like 2 to 18 carbon glycols; trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, polyglycerin and other polyhydric alcohols having 3 to 24 carbon atoms; ammonia, methylamine, ethylamine , Propylamine, butylamine, 2-ethylbutylamine, octylamine, dimethylamine, dipropylamine, dibutylamine, diphenylamine, trimethylamine, triethylamine Diethylenetriamine, amines having 1 to 30 carbon atoms, such as triethylenetetramine; and the like. Among these, the compound having active hydrogen is preferably a monohydric alcohol having 1 to 8 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol; ethylene Glycols having 2 to 4 carbon atoms such as glycol and propylene glycol; polyhydric alcohols having 3 to 6 carbon atoms such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerol and polyglycerol More preferably, methanol, ethanol, propanol, butanol, ethylene glycol, trimethylolpropane, pentaerythritol, sorbitol, and still more preferably ethylene glycol.

As a method for preparing the compound represented by the above formula (3), for example, it is prepared by polymerizing an alkylene oxide having 2 to 18 carbon atoms with water or methyl alcohol, which is a compound having an active hydrogen atom, by a usual method. The method of performing etc. can be applied suitably. The alkylene oxide and the compound having an active hydrogen atom may be used alone or in combination of two or more.

The alkylene oxide having 2 to 18 carbon atoms preferably contains ethylene oxide, and may contain propylene oxide which can be copolymerized if necessary. Furthermore, in addition to the alkylene oxide having 2 to 18 carbon atoms, other alkylene oxides such as styrene oxide may be additionally contained as necessary.

It does not specifically limit as a polymerization method in preparation of the compound represented by the said Formula (3), For example, it is preferable to use a well-known polymerization method in consideration of versatility. In such a polymerization method, it is preferable to use an acid catalyst or an alkali catalyst. Examples of the acid catalyst include metal and metalloid halogen compounds that are Lewis acid catalysts such as boron trifluoride; mineral acids such as hydrogen chloride, hydrogen bromide, and sulfuric acid. Examples of the alkali catalyst include potassium hydroxide, sodium hydroxide, sodium hydride and the like. These may be used alone or in combination of two or more.

In the graft polymer of the second aspect, the polyether compound may include a derivative of the compound represented by the formula (3) together with the compound represented by the formula (3). A derivative of the compound represented by the above formula (3) may be included instead of the represented compound. Examples of the derivative of the compound represented by the above formula (3) include a terminal group converter obtained by converting the terminal functional group of the compound represented by the above formula (3), and the above formula (3). And a cross-linked product obtained by reacting a compound having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group, and a halogen group in one molecule.

Examples of the terminal group converter include, for example, all or some of the hydroxyl groups at the terminal of the compound represented by the above formula (3), (i) fatty acids having 2 to 22 carbon atoms, succinic acid, and succinic anhydride. , Esterified with a dicarboxylic acid such as maleic acid, maleic anhydride, adipic acid and / or its anhydride; (ii) alkoxylated by a dehydrohalogenation reaction using an alkyl halide, ie alkoxypolyoxy Alkylene; (iii) Sulfated with a known sulfating agent such as chlorosulfonic acid, sulfuric anhydride, sulfamic acid, ie, polyoxyalkylene sulfuric acid (salt).

The weight average molecular weight (Mw) of the compound represented by the above formula (3) is 1500 to 50000. Preferably it is 1500-40000, More preferably, it is 2000-35000, More preferably, it is 3000-35000, Most preferably, it is 4000-25000. Further, the degree of dispersion is not particularly limited, and is preferably 1 to 100, for example. More preferably, it is 1.1-10, More preferably, it is 1.1-3. In the present specification, the degree of dispersion means a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
The weight average molecular weight of the compound represented by the above formula (3) can be measured by GPC under the conditions described in Examples described later.

Graft polymerization for preparing the polymer (II) is performed by addition polymerization of an ethylenically unsaturated monomer starting from a graft site generated when a hydrogen atom or a halogen atom is extracted from a polyether compound. Is called.

In the above graft polymerization, some polyether compounds may have many graft sites in the same molecule and others may not exist at all. When a plurality of atoms are extracted from the same carbon atom, the polyether chain is cleaved at that site. The polymerization termination reaction of the ethylenically unsaturated monomer is a chain transfer reaction, disproportionation termination reaction, recombination termination reaction, etc., which is combined with a polyether compound to form a dimer, trimer or the like of the polyether compound. Sometimes you can. For this reason, it is thought that the molecular weight distribution of the obtained hydrophilic graft polymer becomes wide and the dispersity (Mw / Mn) becomes large.

The graft polymerization method is not particularly limited as long as it is a method capable of graft polymerization of an ethylenically unsaturated monomer to a polyether compound. For example, it is preferable to carry out in the presence of a polymerization initiator from the viewpoint that, when the graft ratio is increased, the shrinkage reduction performance of the hydrophilic graft polymer can be improved. The polymerization initiator is not particularly limited. For example, a known radical initiator can be used, but an organic peroxide is particularly preferable from the viewpoint of reactivity and the like.
JP-A-2002-293596 can be referred to for specific examples of organic peroxides and other graft polymerization methods.

The graft polymer obtained by the graft polymerization may be used as it is, but can also be used after being dissolved in a solvent. Examples of the solvent include water and alcohol, but it is preferable to use water. Moreover, you may transform | convert some or all of acid groups and ester groups, such as a carboxyl group and a sulfonic acid group which a hydrophilic graft polymer has, with the compound which has a basic group. Thereby, a hydrophilic graft polymer can also be used as a salt.

Examples of the compound having a basic group include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and lithium hydroxide; sodium carbonate, calcium carbonate, lithium carbonate, and the like. And alkali metal and alkaline earth metal carbonates; amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. These may be used alone or in combination of two or more.

<Third Form: Compound (III)>
In the third form of the compound contained in the shrinkage reducing agent for hydraulic material, the polymer chain (A) derived from the ethylenically unsaturated monomer component and the end of the (poly) alkylene glycol chain (B) are bonded to each other. A copolymer having a structure bonded via (X), wherein the ethylenically unsaturated monomer includes an unsaturated anionic monomer, and the copolymer includes an unsaturated anionic monomer; The proportion of the structural unit derived from the body is 1 to 30 mol with respect to 1 mol of the (poly) alkylene glycol chain, and the weight average molecular weight of the (poly) alkylene glycol forming the (poly) alkylene glycol chain is 1500 to 50000. This is a (poly) alkylene glycol block copolymer.

The (poly) alkylene glycol block copolymer of the third form is a polymer chain (A) derived from a vinyl monomer (ethylenically unsaturated monomer) component containing an unsaturated anionic monomer. And the end of the polymer chain (B) by the (poly) alkylene glycol structural unit are bonded via the binding site (X), thereby exhibiting excellent shrinkage reduction effect can do.
The (poly) alkylene glycol block copolymer of the third form is not particularly limited as long as it has such a structural feature, but a linear polymer chain (B A copolymer having a structure in which only one end of the polymer chain is bonded to the end of the polymer chain (A) derived from the vinyl monomer component containing the unsaturated anionic monomer via the binding site (X). Preferably there is.
The end of the polymer chain (A) that binds to the polymer chain (B) via the binding site (X) may be the main chain end of the polymer chain (A), or the polymer chain (A) When the side chain is bonded to the terminal atom of the main chain, it may be bonded to the end of the side chain, but is preferably the main chain end.

The (poly) alkylene glycol block copolymer has the following formula (4):
_{^{R 9 - (B) n1 -X}} -A (4)
(In the formula, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. (B) _n1 represents (poly) alkylene. Represents a polymer chain composed of glycol structural units, B is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, X represents an organic residue, and A represents an unsaturated anionic monomer. N1 represents the average number of moles of oxyalkylene group added and is a number from 1 to 1000). Is preferred.

In the above formula (4), X located next to one end of the polymer chain (B) _n1 by the (poly) alkylene glycol-based structural unit is a binding site (X), and an unsaturated anion through X A polymer chain A derived from a vinyl monomer component containing a monomer is bonded to a polymer chain (B) _n1 of a (poly) alkylene glycol structural unit. The other end of the polymer chain (B) _n1 based on the (poly) alkylene glycol structural unit has a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. Any of the 20 aryl groups are attached.

Hereinafter, the polymer chain (A) derived from the vinyl monomer component containing the unsaturated anionic monomer, the polymer chain (B) by the (poly) alkylene glycol structural unit, and the bonding site (X) will be described. .

[Polymer chain derived from vinyl monomer component containing unsaturated anionic monomer (A)]
In the third embodiment, the polymer chain (A) derived from the vinyl monomer component containing the unsaturated anionic monomer is polymerized by the vinyl monomer component containing the unsaturated anionic monomer. A structural unit having a structure.
Moreover, if the structural unit which has the structure which the vinyl-type monomer component containing the said unsaturated anionic monomer polymerized becomes a structural unit of the same structure, the structural unit which originates in another monomer will be used. It may be denatured.

Examples of the unsaturated anionic monomer include an unsaturated carboxylic acid monomer (hereinafter also simply referred to as “monomer (a)”), an unsaturated sulfonic acid monomer (hereinafter simply referred to as “mono monomer”). (Also referred to as “mer (b)”) and unsaturated phosphoric acid monomer (hereinafter also simply referred to as “monomer (c)”).
As the monomer (a), for example, the following formula (5);

(In the formula, at least one of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ is —COOM ¹ , and R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the same or different and have a hydrogen atom, carbon number of 1 10 alkyl _{^{group, - (CH 2) zCOOM 2}} (- (CH 2) zCOOM 2 is, COOM ¹ or other _- (CH 2) _zCOOM may form a ² and anhydride) represent, z Represents an integer of 0 to 2. M ¹ and M ² are the same or different and each represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, a quaternary ammonium group, or an organic amine group. The compound represented by this is preferred.
That is, the monomer (a) is an unsaturated carboxylic acid monomer having at least one carboxyl group bonded to a C═C double bond or a salt thereof (—COOM ¹ ).
The structural unit derived from the monomer (a) is a structure in which a polymerizable double bond of the monomer (a) represented by the formula (5) is opened by a polymerization reaction (double bond (C = C) corresponds to a single bond (-C—C—).

In the above formula (5), the groups represented by M ¹ and M ² are a monovalent metal atom, a divalent metal atom, and the organic amine group is a monovalent metal atom in Z ′ of formula (2) described above. The same as the specific examples of the divalent metal atom and the organic amine group. Examples of the trivalent metal atom include aluminum and iron.
Specific examples of the unsaturated carboxylic acid monomer represented by the above formula (5) are the same as those for forming the structural unit (II) represented by the above formula (2). Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and salts thereof are preferable from the viewpoint of polymerizability, and acrylic acid, methacrylic acid and salts thereof are particularly preferable.

Examples of the monomer (b) include styrene sulfonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts or substituted amine salts thereof; sulfone ethyl methacrylate, sulfopropyl methacrylate, sulfobutyl methacrylate. , Sulfoalkyl (meth) acrylates such as sulfoethyl acrylate, sulfopropyl acrylate or sulfobutyl acrylate, or alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts or substituted amine salts thereof; 2-acrylamide-2 -Methylpropanesulfonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts or substituted amine salts thereof are used. Preferably, it is styrene sulfonic acid or sulfoalkyl (meth) acrylate, or a salt thereof. The salt is preferably an alkali metal salt.

Examples of the monomer (c) include hydroxyalkyl (meth) acrylate monophosphate esters such as hydroxyethyl methacrylate monophosphate ester, hydroxyethylpropyl methacrylate monophosphate ester, hydroxyethylbutyl methacrylate monophosphate ester, and alkalis thereof. Metal salts, alkaline earth metal salts, ammonium salts, amine salts, substituted amine salts and the like are used.
Two or more of these unsaturated anionic monomers may be used in combination.

The vinyl monomer component containing the unsaturated anionic monomer may contain a vinyl monomer other than the unsaturated anionic monomer.
As the vinyl monomer other than the unsaturated anionic monomer, in addition to the compounds mentioned as specific examples of the monomer forming the other structural unit (III) in the compound of the first form, Esters of unsaturated monocarboxylic acids such as methyl (meth) acrylate and glycidyl (meth) acrylate and alcohols having 1 to 30 carbon atoms; polyethylene glycol mono (meth) acrylate, methoxy (poly) ethylene glycol mono (meth) Various (alkoxy) (poly) alkylene glycol mono (meth) acrylates such as acrylate; diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and alcohols having 1 to 30 carbon atoms; Diamides of unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; Diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to coal or amine and the above unsaturated dicarboxylic acids; (poly) ethylene glycol di (meth) acrylate, ( (Poly) alkylene glycol di (meth) acrylates such as poly) propylene glycol di (meth) acrylate; (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; (methoxy) polyethylene glycol monovinyl ether, (methoxy) polyethylene Vinyl ethers such as glycol mono (meth) allyl ether or (meth) allyl ethers; 3-methoxy-3-butenyl ethers such as (methoxy) polyethylene glycol 3-methyl-3-butenyl ether And the like, may contain these one or more.

It is preferable that the vinyl-type monomer component containing the said unsaturated anionic monomer contains 1-100 mass% of unsaturated anionic monomers with respect to 100 mass% of the whole vinyl monomer component. More preferably, it is 10 to 100% by mass, still more preferably 50 to 100% by mass, and most preferably 100% by mass, that is, the vinyl monomer component is composed only of unsaturated anionic monomers. It is to become.

In the (poly) alkylene glycol block copolymer according to the third embodiment, the ratio of the structural unit derived from the unsaturated anionic monomer to 1 mol of the (poly) alkylene glycol chain, that is, the unsaturated anionic monomer The average number of moles of units introduced is 1-30.
By setting the average number of introduced moles to 1 or more, the copolymer can sufficiently exhibit the performance based on the polymer chain (A) based on the unsaturated anionic monomer unit.
On the other hand, when the average number of moles introduced exceeds 30, the dispersibility develops, so that it becomes impossible to add a shrinkage reducing agent necessary for obtaining sufficient shrinkage reducing properties.
The average number of moles introduced is preferably 1-20, more preferably 2-15, and even more preferably 2-10.

In the (poly) alkylene glycol block copolymer according to the third embodiment, an unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A), and a polyalkylene glycol chain It is preferable that a mass ratio with (B) is 0.3-70 / 99.7-30. When the mass proportion of the unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A) is less than 0.3% by weight, a (poly) alkylene glycol block copolymer May not sufficiently act on the hydraulic material and the shrinkage reduction performance may not be sufficient. If it exceeds 70% by weight, the (poly) alkylene glycol block copolymer may increase the retarding property of the hydraulic material. There is. The mass ratio is preferably 0.5 to 65 / 99.5 to 35, more preferably 1 to 60/99 to 40, still more preferably 3 to 60/97 to 40, and particularly preferably 5 -60 / 95-40.

In the (poly) alkylene glycol block copolymer in the third embodiment, the monomer component that is the raw material of the compound is a monomer component that forms the polymer chain (A) and a polyalkylene glycol chain ( B). That is, an ethylenically unsaturated monomer component (a vinyl monomer other than the unsaturated anionic monomer and the unsaturated anionic monomer) forming the polymer chain (A), and a polyalkylene glycol chain (B), the number of moles of unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A), and the number of moles of polyalkylene glycol chain (B) The ratio with the number of moles of vinyl monomers other than unsaturated anionic monomers is preferably 25 to 97/75 to 3/0 to 72. More preferably, it is 50-97 / 50-3 / 0-47, More preferably, it is 65-95 / 35-5 / 0-30, Especially preferably, 80-95 / 20-5 / 0 15.

[Polymer chain (B) by (poly) alkylene glycol structural unit]
The polymer chain (B) of the (poly) alkylene glycol-based structural unit is preferably a polymer chain ((poly) alkylene oxide) composed of an alkylene oxide having 2 to 18 carbon atoms. Hereinafter, (poly) alkylene glycol is also referred to as PAG.
More preferably, it is an alkylene oxide having 2 to 8 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene. Examples include monooxide and octylene oxide. In addition, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide Epoxides and the like can also be used.

The alkylene oxide constituting the (poly) alkylene glycol structural unit is mainly a relatively short-chain alkylene oxide (oxyalkylene group) having about 2 to 8 carbon atoms from the viewpoint of affinity with cement particles. Is preferred. More preferably, the main component is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and still more preferably, the main component is ethylene oxide.

The “main body” as used herein means that when the polymer chain (B) of the (poly) alkylene glycol structural unit is composed of two or more types of alkylene oxides, It means that it occupies the majority in the number of existence. When “dominating” is expressed in terms of mol% of ethylene oxide in 100 mol% of all alkylene oxides, 50 to 100 mol% is preferable. Thereby, the (poly) alkylene glycol block copolymer in the present invention has higher hydrophilicity. More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more, Especially preferably, it is 80 mol% or more, Most preferably, it is 90 mol% or more.

When the polymer chain (B) with the (poly) alkylene glycol structural unit is composed of two or more kinds of alkylene oxides, any form such as random addition, block addition, and alternate addition of two or more kinds of alkylene oxides. May be added.

When the polymer chain (B) by the (poly) alkylene glycol-based structural unit contains an alkylene oxide having 3 or more carbon atoms, the (poly) alkylene glycol-based block copolymer in the third embodiment is used. Since it is possible to impart some degree of hydrophobicity, when the above copolymer is used as a shrinkage reducing agent, it gives some structure (network) to the cement particles, and the viscosity and stiffness of the cement composition Can be reduced. On the other hand, if an alkylene oxide having 3 or more carbon atoms is introduced too much, the hydrophobicity of the copolymer becomes too high, so that the water-solubility is lost and the workability is significantly reduced. Since it becomes easy to act, there exists a possibility of becoming the factor of the fall of the freeze-thaw resistance resulting from the fall of the air quantity adjustability of concrete and mortar. For this reason, it is preferable that content of C3 or more alkylene oxide with respect to 100 mass% of all alkylene oxides is 50 mass% or less. More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, Most preferably, it is 10 mass% or less.

Here, from the viewpoint of improving hydrolysis resistance, an oxyalkylene group having 3 or more carbon atoms may be introduced at the terminal of the polymer chain (B) by the (poly) alkylene glycol structural unit.
Examples of the oxyalkylene group having 3 or more carbon atoms include an oxypropylene group, an oxybutylene group, an oxystyrene group, and an alkyl glycidyl ether residue. Of these, an oxypropylene group and an oxybutylene group are preferable because of ease of production.
When introducing the oxyalkylene group having 3 or more carbon atoms, the amount introduced is preferably adjusted in consideration of the hydrolysis resistance of the binding site (X) in the block copolymer of the present invention. The amount introduced is preferably 50 mol% or more with respect to the polymer chain (B) of the (poly) alkylene glycol structural unit. More preferably, it is 100 mol% or more, More preferably, it is 150 mol% or more, Especially preferably, it is 200 mol% or more.

In the (poly) alkylene glycol block copolymer in the third embodiment, the average number of repeating alkylene oxides in the polymer chain (B) (average number of added moles of oxyalkylene group) is 1-1000. preferable.
When the average number of added moles of the oxyalkylene group is 1 or more, the copolymer can sufficiently exhibit the performance based on the polymer chain (B) by the (poly) alkylene glycol structural unit. .
In addition, when the average number of added moles of the oxyalkylene group exceeds 1000, the viscosity of the raw material compound used for producing the copolymer is increased, and the reactivity is not sufficient. There is a possibility that it may not be suitable in terms of points.
The lower limit of the average added mole number is more preferably 10, still more preferably 20, still more preferably 50, particularly preferably 75, particularly more preferably 80, and most preferably 100. It is. The upper limit is more preferably 800, still more preferably 700, even more preferably 600, particularly preferably 500, particularly more preferably 300, and most preferably 200.
The average number of repeating alkylene oxides (average number of moles of oxyalkylene group added) means the average number of moles of alkylene oxide added in one branch.

Among the polymer chains (B) of the (poly) alkylene glycol block copolymer in the third embodiment, the ends of those not bonded to the polymer chain (A) via the binding site (X) are: It is preferably any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. More preferably, a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, phenol, methylphenol, naphthol Either.
R ⁹ in the above formula (4) is preferably any one of these.

The (poly) alkylene glycol compound that forms the polymer chain (B) in the (poly) alkylene glycol block copolymer in the third embodiment has a surface tension of 55 to 70 mN / m measured under the following conditions. It is preferable that. The surface tension of the (poly) alkylene glycol compound is more preferably 55 to 65 mN / m, still more preferably 57 to 65 mN / m.
<Surface tension measurement conditions>
Sample solution: 5% by mass aqueous solution of (poly) alkylene glycol compound Measuring instrument: Dynamic surface tension meter (SITAS Science line t60 (manufactured by MESSTECHNIK))
<Measurement procedure>
(1) Put 200 parts by mass of ion-exchanged water at 25 ° C. into a 300 ml glass beaker containing a stirrer chip having a length of 39 mm, and adjust the temperature in an atmosphere at 25 ° C. while stirring with a magnetic stirrer. 100 parts by mass of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. is charged. After the addition, the number of revolutions is set to 700 rpm, and the mixture is stirred for 30 minutes so that water-soluble components in the cement particles are sufficiently eluted in water, and then allowed to stand for 10 minutes. The supernatant was filtered with suction using filter paper (Advantech Toyo Co., Ltd., quantitative filter paper 5C). Thus, a cement supernatant aqueous solution is obtained. Place the adjusted cement supernatant in a container, seal with nitrogen, seal tightly and store.
(2) On the other hand, ion exchange water at 25 ° C. is added to (poly) alkylene glycol for measuring the surface tension to prepare an aqueous solution having a solid content concentration of 15% by mass. 15 parts by mass of an aqueous solution containing this compound is added to 30 parts by mass of the cement supernatant and mixed well to prepare a 5% by mass sample aqueous solution. The sample aqueous solution is put in a container, sealed with nitrogen, sealed, and adjusted to 20 ° C.
(3) Using a dynamic surface tension meter (SitaScience line t60 (manufactured by MESSTECHNIK)), the surface tension of the (poly) alkylene glycol 5 mass% aqueous solution adjusted to 20 ° C. was measured. The value measured at Frequency 0.5 Hz is the surface tension of the corresponding compound.

[Binding site (X)]
In the (poly) alkylene glycol block copolymer according to the third embodiment, the bonding site (X) has a structure capable of chemically and stably bonding the polymer chain (A) and the polymer chain (B). The structure is not particularly limited as long as it has a site.
As a preferable structure of the binding site, an organic residue derived from a structure serving as a chain transfer agent used in a polymerization reaction can be given.
Examples of binding site (X) include (i) a binding site containing a sulfur atom, (ii) a binding site derived from an azo initiator, (iii) a binding site derived from a residue containing a phosphorus atom, (iv) other Examples include structure-derived binding sites.
The structures of the organic residues present at a plurality of binding sites may be the same or different.

(I) Bonding Site Containing Sulfur Atom As the binding site (X) containing a sulfur atom, a structure that forms an ester bond with the terminal oxygen atom of the polymer chain (B) and contains a sulfur atom, and a polymer There is a structure that does not form an ester bond with the terminal oxygen atom of the chain (B) and contains a sulfur atom.
As the bonding site (X) containing the sulfur atom, for example, the following formula (6):

(In the formula, R ¹⁴ is an organic residue, preferably a linear or branched alkylene group having 1 to 18 carbon atoms, phenyl group, alkylphenyl group, pyridinyl group, thiophene, pyrrole, furan, thiazole, etc. Of the aromatic group (which may be partially substituted with a hydroxyl group, amino group, cyano group, carbonyl group, carboxyl group, halogen group, sulfonyl group, nitro group, formyl group, etc.)). Can be mentioned.

R ^{14 in the} structure represented by the above formula (6) is a site bonded to the polymer chain (B) by the (poly) alkylene glycol structural unit, and the sulfur atom (S) contains an unsaturated anionic monomer. It is a site | part couple | bonded with the polymer chain (A) derived from a vinyl-type monomer component.

That the bonding site (X) does not form an ester bond with the terminal oxygen atom of the polymer chain (B) means that R ^{14 of the} structure represented by the formula (6) is a polymer composed of a (poly) alkylene glycol structural unit. When bonded to the terminal oxygen atom of the chain (B), the following formula (7):

(Wherein R ¹⁴ is the same as described above), but this does not include an ester bond.
Such a structure has a terminal thiol obtained by tosylation of the terminal hydroxyl group of the polymer chain (B) with a (poly) alkylene glycol structural unit, thioacetylation with thioacetic acid, and hydrolysis, as described later. It can be formed by subjecting the unsaturated carboxylic acid monomer (a) to block polymerization using a radical polymerization initiator with a group as a chain transfer agent.

On the other hand, the copolymer caused a dehydration esterification reaction between the carboxyl group of mercaptocarboxylic acid and the hydroxyl group at the terminal of the polymer chain (B) by the (poly) alkylene glycol structural unit, and thus obtained. When the thiol ester is used as a chain transfer agent and obtained by block polymerization of the unsaturated carboxylic acid monomer (a) using a radical polymerization initiator, the bonding site (X) is represented by the following formula (8):

(In the formula, R ¹⁵ is a mercaptocarboxylic acid residue, for example, a linear or branched alkylene group having 1 to 18 carbon atoms, phenyl group, alkylphenyl group, pyridinyl group, thiophene, pyrrole, furan, thiazole, etc. Aromatic groups (however, they may be partially substituted with a hydroxyl group, amino group, cyano group, carbonyl group, carboxyl group, halogen group, sulfonyl group, nitro group, formyl group, etc.)). .
In this case, the binding site includes the terminal oxygen atom of the polymer chain (B) by the (poly) alkylene glycol structural unit and the following formula (9):

(Wherein R ¹⁵ is the same as described above), and an ester bond is included at this site.

(Ii) Binding site derived from an azo initiator The binding site derived from an azo initiator is a site derived from a polymerization initiator (azo initiator) containing an azo group, for example, as shown in the following formula (10) A structure derived from an azo initiator is preferred.

(Wherein R ¹⁶ are independently of each other an alkylene group having 1 to 20 carbon atoms (the alkylene group is partially substituted with an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, etc.) ), A carbonyl group or a carboxyl group, or an alkylene group having 1 to 20 carbon atoms (the alkylene group is an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, etc.). Is a group bonded to a carbonyl group or a carboxyl group, and R ¹⁷ is independently of each other an alkyl group having 1 to 20 carbon atoms or a carboxy substitution (having 1 to 10 carbon atoms). an alkyl group, a phenyl group or substituted phenyl group, R ^18, independently of one another, a cyano group, an acetoxy group, a carbamoyl group or (C 1 -C 10 is a alkoxy) carbonyl group.) The azo initiators include having a repeating unit represented by.
More preferably, the azo initiator shown by following formula (11) is mentioned.

The azo initiator represented by the above formula (11) preferably has a structure in which the terminal is previously bonded to the polymer chain (B) of the (poly) alkylene glycol structural unit by an ester bond.

The structure of the organic residue X as a binding site derived from the azo initiator represented by the above formulas (10) and (11) is a structure represented by the following formulas (12) and (13).

^(Wherein, R ^16, R ^{17, R 18} are the same as ^{R 16,} R ^{17, R 18} in formula (10).)

The carbon of the carbonyl group in Formula (13) is the side bonded to the polymer chain (B) by the (poly) alkylene glycol structural unit.

(Iii) Binding site derived from a residue containing a phosphorus atom Examples of the binding site containing a phosphorus atom include the following formula (14):

(Wherein, Y1 is .M ³ representing an organic residue of the metal atom, an ammonium group or an organic amine group) structure is preferably represented by.
Y1 is a site that binds to the polymer chain (B) by the (poly) alkylene glycol-based structural unit, and the phosphorus atom of hypophosphorous acid (salt) that binds to Y1 is high due to the unsaturated anionic monomer unit. This is the site that binds to the molecular chain (A).

Examples of the organic residue include a linear, branched or cyclic alkylene group having 2 to 30 carbon atoms, and a divalent aromatic group having 6 to 30 carbon atoms (phenylene group, alkylphenylene group, and pyridine, Thiophene, pyrrole, furan, divalent group derived from thiazole, etc.), for example, hydroxyl group, amino group, acetylamino group, cyano group, carbonyl group, carboxyl group, halogen group, sulfonyl group, nitro group, formyl A group which may be partially substituted with a substituent such as a group is preferred.
Among these, more preferably, a divalent organic residue having 2 to 18 carbon atoms and a part thereof are substituted with a hydroxyl group, and more preferably a linear or branched chain having 2 to 8 carbon atoms. -Like alkylene groups and some of them are substituted with hydroxyl groups.

The hypophosphite is preferably a salt formed by hypophosphorous acid and any one of a metal, ammonia or an organic amine. As the metal, an alkali metal, an alkaline earth metal or the like is preferable. Examples of organic amines include alkylamines having 1 to 18 carbon atoms, hydroxyalkylamines, polyalkylenepolyamines, and the like. Among these, a salt formed by sodium, potassium, ammonia, or triethanolamine is preferable.

(Iv) Binding sites derived from other structures Specific examples of the binding sites derived from other structures include the following binding sites derived from chain transfer agents. Among these, those having a sulfur atom are also included in the above (i) binding site containing a sulfur atom.
For example, after reacting a thiocarboxylic acid such as thioacetic acid or thiobenzoic acid with zinc halide to the -OH group at the end of (poly) alkylene glycol, an alkali hydrolysis is performed to convert the -OH group. Compound converted to -SH group; after reacting diethyl azodicarboxylate (DEAD) with triphenylphosphine in the presence of (poly) alkylene glycol and thioacetic acid, alkaline hydrolysis is performed to obtain (poly) Compound obtained by converting —OH group at the terminal of alkylene glycol to —SH group; and —OH group at the terminal of (poly) alkylene glycol is subjected to SN2 reaction with allyl halide such as allyl bromide, to the terminal of (poly) alkylene glycol Compound having allyl group; Compound having double bond such as allyl group at the terminal of (poly) alkylene glycol To, thioacetic acid, after addition of thiocarboxylic acid such as thiobenzoic acid, by performing alkaline hydrolysis, the compound was converted to -SH group;
These compounds (chain transfer agents) may be used alone or in combination of two or more.

Among the various structures described above, the binding site (X) is preferably (i) a binding site containing a sulfur atom.
When the binding site (X) is a binding site containing a sulfur atom, the sulfur atom content in the entire (poly) alkylene glycol block copolymer in the present invention is preferably 0.001% by mass or more. . More preferably, it is 0.005 mass% or more, More preferably, it is 0.01 mass% or more. Moreover, it is preferable that content of a sulfur atom will be 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less.
The sulfur atom content can be calculated from the sulfur atom content in the PAG thiol compound and the average value of the number of vinyl monomer units in the polymer chain (A) with respect to one thiol group (SH). When the sulfur atom content is within the above range, the (poly) alkylene glycol block copolymer in the third embodiment can be more efficiently produced by the production method described later.

As a preferable form of the (poly) alkylene glycol block copolymer in the third form, a polymer chain (A) and a polymer chain (A) after 15 minutes in a 2% by weight alkaline aqueous solution of the copolymer ( The decomposition rate into B) is 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 2 mass% or less. Most preferably, it is substantially 0% by mass.
The decomposition rate here is a hydrolysis rate in an alkaline aqueous solution, and when the hydrolysis rate is 10% by mass or less, more excellent performance as a shrinkage reducing agent is exhibited.
From the viewpoint of lowering the hydrolysis rate, the bonding site (X) is preferably a non-ester bond having a sulfur atom.
Thus, it is one of the preferred embodiments of the present invention that at least one of the bonding sites (X) is a non-ester bond having a sulfur atom.

The hydrolysis rate can be measured by, for example, the following hydrolysis test.
(1) The weight average molecular weight (Mw) of the copolymer is measured under the GPC measurement conditions described later, and is defined as the molecular weight before the reaction (before decomposition).
(2) The copolymer is dissolved in an aqueous NaOH solution to prepare a 2% by mass aqueous solution. At that time, the pH of the NaOH aqueous solution is adjusted in advance so that the pH of the aqueous solution becomes 12.5. The 2 mass% aqueous solution is stirred for 15 minutes, and then neutralized with 35% HCl aqueous solution to adjust the pH to 5.0.
The copolymer is taken out, and its weight average molecular weight (Mw) is measured under the GPC measurement conditions described later to obtain a molecular weight after reaction (after decomposition).
(3) The hydrolysis rate is calculated from the GPC chart before and after the reaction.

Among the (poly) alkylene glycol block copolymers in the third embodiment, particularly preferred structures are structures represented by the following formulas (15) and (16), respectively.

(In the formulas (15) and (16), R ¹⁹ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ²⁰ is the same or different and represents a hydrogen atom or a methyl group, and n5 represents the average number of added moles of an oxyethylene group, and is a number of 1 to 500 (preferably a number of 75 to 500). m3 is a number of 1 to 500 (preferably a number of 1 to 30).
In the structures of the above formulas (15) and (16), the unsaturated carboxylic acid monomer is acrylic acid or methacrylic acid, the (poly) alkylene glycol chain is a (poly) ethylene glycol chain, and the binding site (X) is thio A structure that is a binding site containing a sulfur atom derived from acetic acid or a metal salt thereof is preferable.

The above formula (15), (16), the position of ^{R 20} and COOH groups of the unsaturated carboxylic acid monomer units depicts a hydrogen atom side of the terminal but, ^{R 20} in each monomer unit And the position of COOH group may be located in the sulfur atom side. In the structures represented by the above formulas (15) and (16), whether the position of R ²⁰ and the COOH group is on the hydrogen atom side or the sulfur atom side is randomly determined for each monomer unit.

[Method for Producing (Poly) alkylene Glycol Block Copolymer]
As an example of the method for producing the (poly) alkylene glycol block copolymer of the third aspect, a copolymer having a binding site containing a sulfur atom derived from thioacetic acid (or a metal salt thereof) is produced. This will be described below.

The (poly) alkylene glycol block copolymer according to the third embodiment prepares a polymer chain (B) with a (poly) alkylene glycol structural unit having a hydroxyl group terminal at at least one terminal, and the hydroxyl group A step of tosylation reaction on the base end (tosylation step), a step of reacting thioacetic acid or its metal salt to perform thioacetylation reaction (thioacetylation step), and a thioacetyl group obtained by thioacetylation step Step of decomposing (hydrolysis step), unsaturated vinyl monomer using radical polymerization initiator as polymer chain (B) by (poly) alkylene glycol structural unit having thiol group at terminal Can be produced by carrying out a block polymerization step (block polymerization step).
The polymer chain (B) composed of a (poly) alkylene glycol structural unit having a thiol group at one or both ends is also referred to as a PAG (di) thiol compound. When (poly) alkylene glycol is (poly) ethylene glycol, it is also called a PEG (di) thiol compound.

[Tosylation process]
In the tosylation step, a tosyl group is generated by reacting a hydroxyl group end of a polymer chain with a (poly) alkylene glycol-based structural unit having a hydroxyl group end and a tosylating agent to form a tosylated (poly) alkylene glycol. A polymer chain is obtained from the system structural unit.
The tosylating agent used in the tosylation step and the reaction conditions are not particularly limited as long as the hydroxyl group can be tosylated. For example, tosyl chloride (TsCl) is used as a tosylating agent and dichloromethane (CH ₂ Cl ₂ ) is reacted. What is necessary is just to set reaction conditions suitably as a solvent.

[Thioacetylation process]
In the thioacetylation step, the tosyl group of the polymer chain obtained by the (poly) alkylene glycol-based structural unit having a tosyl group at the end obtained by tosylation of the hydroxyl group obtained by the tosylation step is reacted with the thioacetylating agent. To produce a thioacetyl group to obtain a polymer chain comprising a thioacetylated (poly) alkylene glycol structural unit.
The thioacetylating agent used in the thioacetylating step and the reaction conditions are not particularly limited as long as the tosyl group can be thioacetylated. For example, potassium thioacetate (CH ₃ COSK) is used as the thioacetylating agent, and acetonitrile (CH ₃ CN) is used. May be used as a reaction solvent, and reaction conditions may be set as appropriate.

[Hydrolysis step]
In the hydrolysis step, the thioacetyl group of the polymer chain is hydrolyzed by the (poly) alkylene glycol structural unit having a thioacetyl group at the end obtained by the thioacetylation step and having a thioacetyl group at the end. To obtain a polymer chain composed of (di) thiolated (poly) alkylene glycol structural units. For example, PAG (di) thiol compounds represented by the following formulas (17) and (18) can be obtained.
PAG (di) thiol compounds represented by the following formulas (17) and (18) are preferable as intermediates for producing the (poly) alkylene glycol block copolymers according to the present invention.
In the hydrolysis step, reaction conditions may be set as appropriate so that hydrolysis of the thioacetyl group proceeds.

(In formulas (17) and (18), R ⁹ , R ¹⁴ and n1 are the same as described above. AO represents an oxyalkylene group.)

[Block polymerization process]
As described above, the PAG (di) thiol compound has a function as a chain transfer agent. By using this compound as a chain transfer agent, radical polymerization of the vinyl monomer component described above is performed. The (poly) alkylene glycol block copolymer of the third form can be produced simply and efficiently at a low cost.
Of the unsaturated anionic monomers contained in the vinyl monomer component, the unsaturated carboxylic acid monomer (monomer (a)) forming the polymer chain (A) is preferably the main component, It is preferable that substantially all are unsaturated carboxylic acid monomers forming the polymer chain (A).

The polymer obtained by the above polymerization reaction is easy to handle by adjusting it to a pH range of weak acid or higher (preferably pH 4 or higher, more preferably pH 5 or higher, particularly preferably pH 6 or higher) in an aqueous solution state. be able to.
On the other hand, when the polymerization reaction is carried out at a pH of 7 or more, the polymerization rate is lowered, and at the same time, the copolymerizability is not sufficient and the performance as a shrinkage reducing agent may not be sufficiently exhibited. Therefore, in the polymerization reaction, it is preferable to perform the polymerization reaction in a pH range from acidic to neutral (preferably less than pH 6, more preferably less than pH 5.5, and still more preferably less than pH 5).

[Method for producing a copolymer having a binding site other than a binding site containing a sulfur atom]
So far, an example in the case of producing a copolymer having a binding site containing a sulfur atom has been described. A method for producing a copolymer having another structure as a binding site will be described below.

In the case of producing a copolymer having a binding site derived from an azo initiator, as a starting material, a structure in which the terminal of the azo initiator is previously bonded to a polymer chain (B) by a (poly) alkylene glycol structural unit by an ester bond Can be used.
Those having a structure in which the terminal of the azo initiator is preliminarily bonded to the polymer chain (B) by the (poly) alkylene glycol structural unit by an ester bond include, for example, an azo initiator having carboxyl groups at both ends of the azo group ( It can also be obtained by esterifying V-501 or the like (manufactured by Wako Pure Chemical Industries, Ltd.) and (poly) alkylene glycol. As a method of esterification, since a azo initiator will decompose | disassemble when a heating process is performed, the manufacturing method which does not include a heating process is required. As such a production method, (1) a method in which an azo initiator is reacted with thionyl chloride to synthesize an acid chloride, and then a (poly) alkylene glycol is reacted to obtain an azo initiator; (2) an azo initiator And (poly) alkylene glycol using decyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine as required to obtain an azo initiator by dehydration condensation.

When the azo initiator is used, the azo group is decomposed by heat to generate radicals, from which polymerization starts. Therefore, unsaturated anionic monomers are successively added to one end of the polyalkylene oxide moiety comprising an oxyalkylene group to form the (poly) alkylene glycol block copolymer of the third preferred form. The

When producing a copolymer having a bonding site derived from a residue containing a phosphorus atom, an organic residue having a carbon-carbon double bond at the terminal oxygen atom of the polymer chain (B) by the (poly) alkylene glycol structural unit. It is preferable to produce a phosphorus atom-containing (poly) alkylene glycol compound by adding hypophosphorous acid (salt) to compound C having a structure in which groups are bonded.

The compound C can be synthesized by a known method.
The compound C may be synthesized by a method in which a compound having an unsaturated group is added to the polymer chain (B) of the (poly) alkylene glycol structural unit. As the form of addition, known methods such as esterification, etherification and amidation can be used. The unsaturated compound to be added may be any compound that can be added to the alkylene oxide.

In the step of subjecting compound C to hypophosphorous acid (salt) addition reaction, hypophosphorous acid (salt) is added in an amount of 0.01 to 100 mol with respect to 1 mol of unsaturated bond contained in compound C. It is preferable to add and react. From the viewpoint of increasing the reaction rate of the compound C, hypophosphorous acid (salt) is preferably 0.1 mol or more, more preferably 0.2 mol or more, and still more preferably 0 with respect to 1 mol of the compound C. .5 moles or more. From the viewpoint of reducing unreacted hypophosphorous acid (salt), hypophosphorous acid (salt) is preferably 10 mol or less, more preferably 5 mol or less, and still more preferably 1 mol of compound C. 2 mol or less.

The step of subjecting compound C to the addition reaction of hypophosphorous acid (salt) is preferably performed at a temperature of 0 to 200 ° C. More preferably, it is performed at a temperature of 20 to 150 ° C, more preferably 40 to 120 ° C, and still more preferably 50 to 100 ° C.

After the step of subjecting compound C to hypophosphorous acid (salt) addition reaction, it is preferable to purify the obtained phosphorus atom-containing (poly) alkylene glycol compound. The purification step can be performed by drying the solution after the reaction to remove the solvent, then suspending in the purification solvent and performing filtration, and extraction, or both.
The purification solvent may be selected as appropriate, and for example, THF, acetonitrile, chloroform, isopropyl alcohol and the like are preferable.
The extraction solvent may be selected as appropriate, but it is preferably carried out using water, methanol, acetonitrile, dioxane or the like as the highly polar solvent. It is preferable to use diethyl ether, cyclohexane, chloroform, methylene chloride or the like as the low polarity solvent.

The step of addition reaction of the compound C and hypophosphorous acid (salt) can be performed in a solution state dissolved in a solvent using a radical polymerization initiator as necessary. Examples of the solvent used in this case include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ethyl acetate and the like. Ester compounds; ketone compounds such as acetone and methyl ethyl ketone; and cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, it is preferable to use water as a solvent.

When performing the addition reaction of the compound C and hypophosphorous acid (salt) using water as a solvent, it is necessary to use a water-soluble radical polymerization initiator to remove insoluble components after the reaction. It is preferable because there is no. For example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; organic peroxides such as t-butyl hydroperoxide; 2,2′-azobis-2-methylpropionamidine hydrochloride, etc. Azoamidine compounds, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, azonitrile compounds such as 2-carbamoylazoisobutyronitrile, 2,4′-azobis { Azoamide compounds such as 2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, macroazo compounds such as esters of 4,4′-azobis (4-cyanovaleric acid) and (alkoxy) polyethylene glycol Water-soluble azo initiators such as these can be used, and one or more of these can be used. Among these, a persulfuric acid-based initiator is preferable.

The phosphorus atom-containing (poly) alkylene glycol-based compound has a function as a chain transfer agent, and the compound is used as a chain transfer agent to radically polymerize an unsaturated anionic monomer. 3 (poly) alkylene glycol block copolymers in a suitable form can be produced simply and efficiently at a low cost.
Since the step of radically polymerizing the unsaturated anionic monomer can be performed in the same manner as the block polymerization step using the PAG thiol compound as a chain transfer agent, detailed description thereof is omitted.

<Fourth Form: Compound (IV)>
The fourth form of the compound contained in the shrinkage reducing agent for hydraulic material is adsorbed to at least one of a metal, a metal compound, and a metal ion at at least two ends of a linear or branched polyalkylene glycol chain. A polyalkylene glycol compound to which an organic residue having a function is bonded, wherein the organic residue is selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group The polyalkylene glycol having at least one functional group and forming a polyalkylene glycol chain has a weight average molecular weight of 1500 to 50000.

A compound in which an organic residue is bonded to at least two ends of a linear or branched polyalkylene glycol chain according to the fourth embodiment (hereinafter also referred to as an organic residue-containing polyalkylene glycol compound) is a polyalkylene glycol. Any other structural site may be included as long as it has at least 3 structural sites of the chain and at least two terminal organic residues of the polyalkylene glycol chain. Moreover, when two or more of these structural sites are included, they may be the same or different.

The organic residue bonded to the end of the polyalkylene glycol chain means an organic residue directly bonded to the end of the polyalkylene glycol chain. Here, the term “end of polyalkylene glycol chain” means that the end of polyalkylene glycol chain having an unmodified end (form in which the end is a hydroxyl group) and the end of polyalkylene glycol chain were modified as described later. Things are included. The structure in which an organic residue is bonded to the end of the polyalkylene glycol chain has a structure in which a hydroxyl group at the end of the polyalkylene glycol chain or a reactive functional group is introduced into the end of the polyalkylene glycol chain, and a modified end, It can be formed by reacting with a compound that provides a residue. The reactive functional group is not particularly limited, and examples thereof include an amino group, a carboxyl group, and an epoxy group. An epoxy group is preferable.

The organic residue is bonded to at least two ends of the polyalkylene glycol chain. When the polyalkylene glycol chain is linear, the organic residue is bonded to both ends of the polyalkylene glycol chain. In the case where the polyalkylene glycol chain is branched, it means that an organic residue is bonded to at least two ends of the main chain end and the branched chain end.

The organic residue is characterized by exhibiting an adsorption ability for at least one of a metal, a metal compound, and a metal ion. Thereby, the organic residue-containing polyalkylene glycol compound of the present invention can be adsorbed to at least one of a metal, a metal compound and a metal ion contained in the cement composition.
The same applies to the form in which the organic residues at at least two terminals of the polyalkylene glycol chain are adsorbed on the same metal compound particle.
Cement particles contained in the cement composition are tricalcium aluminate (C ₃ A: 3CaO · Al ₂ O ₃ ), tetracalcium iron aluminate (C ₄ AF: 4CaO · Al ₂ O ₃ · Fe ₂ O ₃ ). , dicalcium silicate _{(C 2 S: 2CaO · SiO} 2) and tricalcium silicate _{(C 3 S: 3CaO · SiO} 2) metal compounds such as are known to be obtained by set a mosaic. Therefore, when at least two terminal organic residues of the polyalkylene glycol chain adsorb to one cement particle, they adsorb to at least two of the metal compounds constituting the mosaic of the cement particle. It will be.

The organic residue has at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group, and a vinyl monomer It is a group having no carbon-carbon bond derived from the body.
The functional group has an electron donating group having a lone electron pair, and forms a coordination bond with at least one of a metal, a metal compound, and a metal ion, thereby forming at least one of the metal, the metal compound, and the metal ion. Can be adsorbed.

The organic residue preferably has a plurality of functional groups exhibiting adsorption ability for at least one of a metal, a metal compound, and a metal ion. The functional group is more preferably an electron donating group.
When one organic residue has a plurality of electron donating groups, the organic residue can be coordinated to at least one of a metal, a metal compound, and a metal ion through a plurality of coordination sites. That is, the organic residue can bind to at least one of a metal, a metal compound, and a metal ion more strongly due to a chelate effect, and thus is more excellent in the cement dispersion performance deterioration suppressing effect and the drying shrinkage reducing performance of the cement additive. It will be a thing.

The number of functional groups per organic residue is preferably 1-12. More preferably, it is 2-12. When the number of functional groups of the organic residue is preferably 1 to 12, more preferably 2 to 12, the organic residue and at least one of a metal, a metal compound, and a metal ion can be more strongly bonded. More preferably, it is 3-12.

The organic residue is a group having a molecular weight of 700 or less. If the molecular weight of the organic residue is 700 or less, even if the amount of the cement additive used is small, the effects of the present application such as the suppression of lowering of the cement dispersion performance and the reduction of drying shrinkage can be efficiently exhibited. The molecular weight of the organic residue is preferably 500 or less, more preferably 300 or less, and still more preferably 200 or less. The molecular weight of the organic residue is preferably 40 or more, more preferably 60 or more, still more preferably 80 or more, and particularly preferably 100 or more.

The organic residue contained in the organic residue-containing polyalkylene glycol compound of the fourth form preferably has any of a carbonyl group, a hydroxyl group, an amino group, a phosphoric acid group, or a silane group among the functional groups. More preferably, it has any of a carbonyl group, a hydroxyl group, an amino group, or a phosphate group.

The organic residue having the carbonyl group is not particularly limited as long as it has a carbonyl group, and includes an organic residue having a functional group containing a carbonyl group in the structure such as a carboxyl group, an aldehyde group, an ester group, an amide group, or the like. . The functional group having a carbonyl group is preferably a carboxyl group or an amide group.

The organic residue preferably has at least two functional groups selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group. Since such an organic residue can bind to at least one of a metal, a metal compound, and a metal ion more strongly due to a chelate effect, the cement additive is more excellent in suppressing the cement dispersion performance and reducing the drying shrinkage. It will be a thing.

The organic residue is not limited as long as it exhibits an adsorbing ability to at least one of a metal, a metal compound, and a metal ion, but the organic residue preferably has a catechol structure. The organic residue preferably has a pyrrolidone structure. Furthermore, the organic residue preferably has a gluconic acid structure.

It can be confirmed by the following method that the organic residue exhibits an adsorbing ability with respect to at least one of a metal, a metal compound, and a metal ion.
The organic residue-containing polyalkylene glycol compound adsorbed to the metal or the like is filtered off after the organic residue-containing polyalkylene glycol compound and the metal, metal compound or metal ion are dispersed in the solution and then filtered. Is done. Therefore, by conducting quantitative analysis of the total amount of organic carbon in the filtrate and quantifying the organic residue-containing polyalkylene glycol compound that is not adsorbed with the metals etc. contained in the filtrate, The proportion of the organic residue-containing polyalkylene glycol compound adsorbed with the metal or the like with respect to the glycol compound can be determined, and the adsorption ability can be confirmed.

The compound in which an organic residue is bonded to at least two ends of the linear or branched polyalkylene glycol chain of the fourth form is as follows. It is obtained by binding a compound that gives an organic residue as described in detail.

The organic residue is a residue formed by bonding a compound that gives an organic residue to the end of a polyalkylene glycol chain, and the compound that gives the organic residue is not particularly a vinyl monomer. Although it does not restrict | limit, Specifically, the following compounds are mentioned.
Amines such as ethylenediamine, diethylenetriamine, triaminotriethylamine, triethylenetetramine, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetra Ethylenepentamine heptaacetic acid, glycol ether diamine tetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine-N-monoacetic acid, ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N′-dipropionic acid, N- ( 2-hydroxyethyl) -ethylenediamine-N, N ′, N′-triacetic acid, N, N′-bis (2-hydroxybenzyl) -ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N, ', N'-tetrapropionic acid, o, o'-bis (2-aminophenyl) ethylene glycol-N, N, N', N'-tetraacetic acid, o, o-bis (2-aminoethyl) ethylene glycol -N, N, N ', N'-tetraacetic acid, glycine, N, N-bis (2-hydroxyethyl) glycine, trans-1,2-cyclohexanediamine-N, N, N', N'-tetraacetic acid 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid, diethylenetriamine-N, N, N ′, N ″, N ″ -pentaacetic acid, 1,6-hexa Methylenediamine-N, N, N ′, N′-tetraacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, 1,2-diaminopropane-N, N, N ′, N′-tetraacetic acid, Triethylenetetramine-N, N, N ′, N ″, N ''',N'''-aminocarboxylic acids such as hexaacetic acid, glutamic acid, aspartic acid and aminosuccinic acid; hydroxyamines such as triethanolamine;

Tartaric acid, citric acid, 2,5-dihydroxy-tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 5-hydroxy-cyclohexane-1,2,3,4-tetracarboxylic acid, 6-hydroxy-tetrahydrofuran-2 , 3,4,5-tetracarboxylic acid, 1,4-dihydroxy-butane-1,1 ′, 4,4′-tetracarboxylic acid, 1,3-dihydroxy-propane-1,1 ′, 3,3 ′ -Hydroxycarboxylic acids such as tetracarboxylic acid, 2- (4-hydroxyphenyl) -propane-1,1 ', 3,3'-tetracarboxylic acid; hydroxyaminocarboxylic acids such as bicine; oxalic acid, maleic acid, succinic acid Acid, 3-butene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, 1,2,3,4,5,6-cyclohexanehexene Polycarboxylic acids such as carboxylic acids; polyols such as gluconic acid, glucosamic acid, glucoheptonic acid lactone, gluconic acid lactone; tyrone, salicylic acid, sulfosalicylic acid, pyrogallol carboxylic acid, alizarin S, alizarin complexone, kojic acid, 3 -Phenols such as (3,4-dihydroxyphenyl) -L-alanine, 3-hydroxytyramine, DL-adrenaline; imidazoles such as histidine; pyrrolidones such as N-hydroxyethylpyrrolidone; ethylenediamine-N, N, N Aminophosphoric acids such as', N'-tetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid); phosphates; phosphites; phosphonates; phosphinates; 2,3-dimercaptopropanol, unitythiol Thiols such as thioglycolic acid, β-mercaptopropionic acid, dimercaptosuccinic acid, aminoethyl mercaptan, thiooxalic acid, cysteamine; sulfurs such as sodium diethyldithiocarbamate, thiourea, thiocarbazide, thiosemicarbazide; monoalkoxysilane, dialkoxy Silanes such as silane, trialkoxysilane, acyloxysilane, triacyloxysilane; o-phenanthroline; acetylacetone; Eriochrome Black T, 1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3 -O, o'-dihydroxyazos such as naphthoic acid, hydroxynaphthol blue, chalcone, Eriochrome Blue Black B, Eriochrome Blue SE, Eriochrome Red B; 1-pyridylazo-2-naphthol, 4- (2-pyridylazo) -resorcin, 2- (2-pyridylazo) -p-cresol, 1- (2-thiazolylazo) -2-naphthol, 4- (2-thiazolylazo)- Hydroxy such as resorcin, 2- (2-thiazolylazo) -p-cresol, thrin, neothrin, 3- (4-sulfophenylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid sodium salt, naphthylazoxin Azos;

Cresolephthalein complexone, thymolphthalein complexone, xylenol orange, methylthymol blue, pyrocatechol violet, pyrogallol red, brompyrogallol red, chromazurol S, eriochrome cyanine R, glycine thimol blue, glycine resole red, etc. Phthalein and triphenylmethanes; murexide; ginsone; thiourea; dithizone; glyoxal bis (2-hydroxyanil); N-benzoyl-N-phenylhydroxylamine; galocyanine; , Fluorescent metal indicators such as Anisidine Blue, Stilbene Fluoro Blue S, Morin; Variamin Blue B Base, Bind Shedra 'S Green Leuco base, 3,3'-dimethyl-naphthoquinone cytidine, Kakoterin, diphenylcarbazide, like a redox indicator such as diphenyl carbazone.
In introducing the organic residue into the terminal of the polyalkylene glycol, one or more of the above compounds can be used. Among these derivatives of the above compounds, polyalkylene glycol, modified polyalkylene glycol, which will be described later, a compound having a functional group capable of reacting with polyalkylene glycol having an organic residue bonded to one end can be used. .

The organic residue has a structure derived from aminocarboxylic acids, phenols, polyols, pyrrolidones or polycarboxylic acids, that is, aminocarboxylic acids, phenols, polyols, pyrrolidones or polycarboxylic acids are polyalkylenes. It preferably has a residue formed by binding to the end of a glycol chain. More preferably, it has a structure derived from aminocarboxylic acids or phenols.
Among residues derived from aminocarboxylic acids or phenols, aspartic acid, 3- (3,4-dihydroxyphenyl) -L-alanine, 3-hydroxytyramine or DL-adrenaline is bonded to the polyalkylene glycol chain end. More preferably, it is a residue formed by bonding aspartic acid or 3-hydroxytyramine to the polyalkylene glycol chain end.

The method for bonding the compound that gives an organic residue to the terminal of the polyalkylene glycol chain is not particularly limited, and a commonly used method can be employed. For example, when the compound giving an organic residue has a carboxyl group (for example, aminocarboxylic acids, hydroxycarboxylic acids, polycarboxylic acids), the organic residue is introduced by an esterification reaction with a hydroxyl group at a polyalkylene glycol terminal. be able to.
In addition, a modified polyalkylene glycol in which a reactive functional group such as an amino group, a carboxyl group, or an epoxy group is introduced at the terminal of the polyalkylene glycol, and a carboxyl group, a hydroxyl group, an amino group, or the like of a compound that gives an organic residue or a derivative thereof Can be introduced with an amide bond, an ester bond, a covalent bond, or the like. As for these, for example, an epoxy group such as polyethylene glycol diglycidyl ether and an amino group such as aspartic acid and 3-hydroxytyramine are reacted to bond them. In addition, if necessary, the hydroxyl group at the other end of the polyalkylene glycol having an organic residue bonded to one end obtained by adding alkylene oxide to the hydroxyl group, amino group, etc. of the compound giving an organic residue. An amino group, a carboxyl group, an epoxy group, etc. are introduced, and a polyalkylene glycol having organic residues bonded to both ends is obtained by reacting these functional groups with a compound that newly gives the organic residue. You can also.

It is also useful to introduce a phosphonate group by reacting a compound having a phosphonate group at the polyalkylene glycol terminal. In this case, it is preferable to introduce a phosphonate group at the two ends of the polyalkylene glycol, and such a compound is represented by the following formula (19). This compound is obtained, for example, by a Mannich reaction of α, ω-diaminopolyalkylene glycol, formaldehyde, and phosphorous acid.
R ²¹ R ²² NCH ₂ CH ₂ (OA ² ) _n6 CH ₂ CH ₂ R ²³ R ²⁴ (19)
(In the formula, A ² is the same or different and represents an alkylene group having 2 to 18 carbon atoms. R ²¹ , R ²² , R ²³ and R ²⁴ are each independently —CH ₂ —PO (OM ⁴ _{q 2} ). ₂ or -R ^{25. At} least one of R ²¹ and R ²² is —CH ₂ —PO (OM ⁴ _q2 ) ₂ , and at least one of R ²³ and R ²⁴ is —CH ₂ —PO (OM ⁴ ₂ ) R ²⁵ represents a hydrogen atom or an unsaturated or saturated hydrocarbon residue, and M ⁴ is the same or different and represents a hydrogen atom, an alkali metal, an alkaline earth metal, an amine and / or an organic amine residue. .q2 representing the group, M is a hydrogen atom, in the case of any of the alkali metals, alkaline earth metals, amines and / or organic amine residue is 1, if M ⁴ is an alkaline earth metal 1 / 2. n6 is OK This represents the average number of moles added of the salkylene group and is a number from 1 to 1000.)

A ² in the above formula (19) is preferably an ethylene group and / or a propylene group, and more preferably an ethylene group.
R ²⁵ in the above formula (19) is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

When the silane group is introduced by reacting a compound having a silane group at the terminal of the polyalkylene glycol, among the compounds having a silane group, an alkoxysilane having 1 to 10 carbon atoms is preferable, and trialkoxysilane is more preferable. Among them, a compound having a -Si _{(OMe) 3} and / or -Si _(OCH 2 _{CH 3)} 3 is particularly preferred. Examples of the synthesis of such compounds include a reaction of 3- (trialkoxysilyl) propyl isocyanate with polyalkylene glycol or polyalkylene glycol diamine. In the reaction of an isocyanate group with an amine or hydroxy group, a urea or urethane bond is formed, respectively.

When the polyalkylene glycol chain is branched, it has two main chain ends and a branched chain end, so that there are three or more ends. Therefore, it is only necessary that at least two of these ends are modified with an organic residue by introducing an organic residue by reacting the compound that gives the organic residue with at least two ends. The modification rate by the organic residue of the branched polyalkylene glycol chain of the present invention is preferably 20% or more, more preferably 40% or more, more preferably several hundred% of all terminals of the branched polyalkylene glycol chain. Preferably it is 60% or more, particularly preferably 80% or more, and most preferably 100%. If the modification rate by the organic residue of the branched polyalkylene glycol chain of the present invention is 20% or more, it is possible to disperse cement with a smaller amount of cement additive, and to further exhibit a drying shrinkage reduction performance. Can do.

In the organic residue-containing polyalkylene glycol compound of the fourth aspect, the mass ratio of the polyalkylene glycol that forms the polyalkylene glycol chain and the compound that provides the organic residue used to form the organic residue is Polyalkylene glycol that forms an alkylene glycol chain / compound that provides an organic residue used to form an organic residue = 99 to 1/1 to 99 is preferred. More preferably, it is 98-10 / 2-90, More preferably, it is 97-20 / 3-80, Most preferably, it is 97-30 / 3-70.

In the organic residue-containing polyalkylene glycol compound of the fourth aspect, the monomer component that is a raw material of the compound is an organic residue and a polyalkylene glycol that forms a polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound. A compound that gives an organic residue used to form a residue, and gives the number of moles of polyalkylene glycol that forms a polyalkylene glycol chain and the organic residue that is used to form an organic residue. The ratio to the number of moles of the compound is preferably 75 to 3/25 to 97. More preferably, it is 50-3 / 50-97, More preferably, it is 40-3 / 60-97, Especially preferably, it is 35-3 / 65-97, Most preferably, it is 35-5 / 65 ~ 95.

The structure of the polyalkylene glycol chain contained in the organic residue-containing polyalkylene glycol compound of the fourth form may be linear or branched. Moreover, you may have 2 or more types of polyalkylene oxide.
The polyalkylene glycol chain contained in the organic residue-containing polyalkylene glycol compound of the fourth form is preferably a polymer chain (polyalkylene oxide) composed of an oxyalkylene group having 2 to 18 carbon atoms. More preferably, carbon number of an oxyalkylene group is the range of 2-8, More preferably, it is the range of 2-4.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, and octylene oxide. It is done. In addition, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide Epoxides and the like can also be used.

The polyalkylene glycol chain preferably contains an oxyethylene group as an essential component in the oxyalkylene group from the viewpoint of a balance between hydrophilicity and hydrophobicity. The oxyethylene group in 100 mol% of the total alkylene oxide is more preferably 60 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more.

The average added mole number of the oxyalkylene group is preferably in the range of 1 to 1000. The lower limit of the average number of moles added is more preferably 25, still more preferably 40, and particularly preferably 50. The upper limit is more preferably 800, still more preferably 700, particularly preferably 600, particularly preferably 500, still more preferably 300, and most preferably 250.

In the organic residue-containing polyalkylene glycol compound of the fourth form, the weight average molecular weight (Mw) of the polyalkylene glycol forming the polyalkylene glycol chain is 1500 to 50000. Preferably it is 1500-40000, More preferably, it is 2000-35000, More preferably, it is 3000-30000, Most preferably, it is 4000-25000.
Further, the dispersity of the polyalkylene glycol forming the polyalkylene glycol chain is not particularly limited, but is preferably 1 to 100, for example. More preferably, it is 1.1-10, More preferably, it is 1.1-3. In the present specification, the degree of dispersion means a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).
In the organic residue-containing polyalkylene glycol compound of the fourth form, the weight average molecular weight of the polyalkylene glycol forming the polyalkylene glycol chain can be measured by GPC under the conditions described in the examples described later.

In the fourth embodiment of the organic residue-containing polyalkylene glycol compound, the polyalkylene glycol forming the polyalkylene glycol chain is the same as the measurement of the surface tension of the (poly) alkylene glycol compound in the polymer of the third embodiment. It is preferable that the surface tension measured under the conditions is 55 to 70 mN / m. The above (the surface tension of the polyalkylene glycol is more preferably 55 to 65 mN / m, still more preferably 57 to 65 mN / m.

When the polyalkylene glycol chain is branched, for example, a branched polyalkylene glycol is synthesized by a method in which an alkylene oxide is sequentially added to a polyhydric alcohol such as trimethylolpropane, glycerin, polyglycerin, or polyglycidol. be able to.

When the polyalkylene glycol chain is composed of two or more alkylene oxides, two or more alkylene oxides may be added in any form such as random addition, block addition, and alternate addition.

The metal adsorbed by the organic residues at at least two terminals of the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound is not particularly limited. For example, typical elements and groups 8, 9 and 10 of the periodic table are included. And metals classified as group 11 and group 11 transition elements. Preferably, an alkali metal, an alkaline earth metal, a metal element of Group 8, 10, 11, 12, 12, 13, or the like of the periodic table can be used, and more preferably, an alkali metal, an alkaline earth, or the like. Base metals such as metal, zinc, aluminum and iron.

Although the metal ion which the said organic residue adsorb | sucks is not restrict | limited in particular, For example, the ion of the metal classified into a typical element and the transition element of the 8th group, the 9th group, the 10th group, and the 11th group of a periodic table is mentioned. Preferred examples include ions of alkali metals, alkaline earth metals, and metal elements of Group 8, Group 10, Group 11, Group 12, Group 13 and Group 14 of the periodic table, and more preferably, alkali metal, alkali Ions of base metals such as earth metals, zinc, aluminum and iron.

<Fifth Form: Compound (V)>
A fifth form of the compound contained in the shrinkage reducing agent for hydraulic material of the present invention is a polyamine compound having an acid group-containing side chain, wherein the polyamine compound comprises a structural unit derived from an unsubstituted polyamine compound and an unsaturated carboxylic acid. Acid group having a structural unit derived from an acid monomer, and the proportion of the structural unit derived from the unsaturated carboxylic acid monomer is 25 to 99 mol% with respect to 100 mol% of all structural units It is a polyamine compound having a containing side chain.

The polyamine compound of the fifth form is an unsubstituted polyamine obtained by reacting an unsaturated carboxylic acid monomer with an active amine hydrogen of a polyamine compound having a primary and / or secondary amino group in the molecule. It has a structural unit derived from a compound and a structural unit derived from an unsaturated carboxylic acid monomer. That is, the polyamine compound is a compound having a structure in which the active amine hydrogen of the unsubstituted polyamine compound is substituted with a side chain having a carboxyl group as an acid group.
In the fifth aspect of the polyamine compound, the proportion of the structural units derived from the unsaturated carboxylic acid monomer is 25 to 99 mol% with respect to 100 mol% of all structural units. Preferably it is 30-97 mol%, More preferably, it is 50-95 mol%.
Hereinafter, the polyamine compound before the active amine hydrogen is replaced with the acid group-containing side chain is also referred to as an unsubstituted polyamine compound.

The unsubstituted polyamine compound is not particularly limited as long as it has a primary and / or secondary amino group in the molecule, and includes amines having such a group or derivatives thereof. Moreover, as an unsubstituted polyamine compound, 1 type of compounds may be used and 2 or more types may be used. Further, the unsubstituted polyamine compound may have two or more of the following amines or derivatives thereof in the structure.
Examples of the amines include polyalkyleneimines obtained by polymerization or copolymerization of alkyleneimines (for example, ethyleneimine, azetidine, pyrrolidine, piperidine, etc.) such as polyethyleneimine obtained by polymerization of ethyleneimine; Polyamides obtained by condensation of polyalkyleneimines and / or (poly) alkylenepolyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polybasic acids such as sulfuric acid, phosphoric acid and adipic acid Polyamines; polyalkyleneimines and / or polyureapolyamines obtained by the reaction of alkyleneimines with urea; by copolymerization of alkyleneimines with acid anhydrides such as phthalic anhydride. A polyamide polyester polyamine obtained; and polyallylamine obtained by polymerization of allylamine, diallylamine and / or its hydrochloride, polydiallylamine-sulfur dioxide copolymer obtained by copolymerization of diallylamine and / or its hydrochloride and sulfur dioxide, Examples thereof include diallylamine-maleic acid copolymer obtained by copolymerization of diallylamine and / or its hydrochloride and maleic acid.
Examples of the polyamine derivatives include 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. Examples include compounds obtained by addition reaction.
Examples of the unsubstituted polyamine compound include epomine (polyethyleneimine) SP-003, SP-006, SP-012, SP-018, SP-200, SP-110, P-1000 (Nippon Shokubai Co., Ltd.), polyallylamine PAA -03, PAA-05, PAA-08, PAA-15, PAA-15B, PAA-10C, PAA-25 (Nittobo), diallylamine / maleic acid copolymer PAS-410, PAS-410SA (Nittobo) Commercially available products such as Co., Ltd. can also be used.
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, and polyalkyleneimine Polyamide polyamine and polyallylamine are particularly preferable.

The number average molecular weight of the unsubstituted polyamine compound is not particularly limited, but is preferably 1500 to 50000. At this time, if the molecular weight is less than 1500, the average particle diameter of the polyamine compound in the alkaline solution tends to be smaller than 2.2 nm, and thus there is a possibility that sufficient drying shrinkage reduction property cannot be obtained. On the other hand, when the number average molecular weight exceeds 50,000, the unsubstituted polyamine compound becomes too large, and there is a possibility that sufficient drying shrinkage reduction property cannot be obtained. The number average molecular weight of the unsubstituted polyamine compound is more preferably 2000 to 40000, still more preferably 2000 to 35000, and most preferably 2000 to 30,000.
The number average molecular weight of the unsubstituted polyamine compound can be measured by gel permeation chromatography (GPC) under the measurement conditions described in the examples.

The polyamine compound of the fifth form has a carboxyl group derived from an unsaturated carboxylic acid monomer as the acid group of the acid group-containing side chain, but in addition to the carboxyl group, a sulfonic acid group or these You may have a side chain which has monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, etc.
The side chain having a carboxyl group can be produced by reacting an unsaturated carboxylic acid monomer with a polyamine compound.
In addition, when the polyamine compound of the fifth form has an acid group-containing side chain such as a sulfonic acid group as an acid group other than a carboxyl group, a sulfonic acid group or a monovalent thereof is added to an atomic group that reacts with an amino group. It is produced by reacting an acid group-containing compound having a structure in which one or more metal salts, divalent metal salts, ammonium salts, or organic amine salts are bonded (hereinafter also referred to as other acid group-containing compounds) with a polyamine compound. be able to.
Examples of the atomic group (group) that reacts with an amino group include an unsaturated hydrocarbon group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; a glycidyl ether group and an epoxy group on a saturated hydrocarbon group having 1 to 20 carbon atoms. And a group to which any of a group, an isocyanate group, a thioisocyanate group, an aldehyde group, a hydroxy group, or a halogen atom is bonded.

Examples of the unsaturated carboxylic acid monomer include (meth) acrylic acid and maleic acid, and one or more of these can be used.

In the polyamine compound having an acid group-containing side chain of the fifth aspect, the monomer component as a raw material of the compound is an unsubstituted polyamine compound used for forming a polyamine compound having an acid group-containing side chain And compounds used to form side chains (unsaturated carboxylic acid monomers, other acid group-containing compounds, and compounds for introducing other side chains other than acid group-containing side chains) is there.
The amount of the unsaturated carboxylic acid monomer used as the monomer component is preferably 0.01 to 1 mole per active amine hydrogen of the unsubstituted polyamine compound. More preferably, it is 0.01-0.8 mol, More preferably, it is 0.01-0.6 mol, Most preferably, it is 0.05-0.6 mol, Most preferably, it is 0. .1 to 0.5 mol.

It is preferable that the usage-amount of the said acid group containing compound is a ratio of 0-0.5 mol per active amine hydrogen of an unsubstituted polyamine compound. More preferably, it is 0-0.3 mol, More preferably, it is 0.01-0.3 mol, Especially preferably, it is 0.05-0.3 mol, Most preferably, it is 0.1 ~ 0.25 mol.

In the polyamine compound having an acid group-containing side chain of the fifth aspect, an unsubstituted polyamine compound used for forming a polyamine compound having an acid group-containing side chain and an acid group-containing side chain are used. The ratio by mass of the acid group-containing compound to be used is as follows: Unsubstituted polyamine compound used to form a polyamine compound having an acid group-containing side chain / acid group-containing compound used to form an acid group-containing side chain = 99 It is preferable that it is 9-50 / 0.1-50. When the mass ratio of the acid group-containing compound used to form the acid group-containing side chain is less than 0.1% by weight, the polyamine compound having the acid group-containing side chain is less likely to act on the hydraulic material and shrinkage is reduced. The performance may be insufficient, and if it exceeds 50% by weight, the curing delay of the hydraulic material may increase due to the polyamine compound having an acid group-containing side chain. The mass ratio is more preferably 99.8 to 55 / 0.2 to 45, still more preferably 99.7 to 60 / 0.3 to 40, and particularly preferably 99.7 to 65/0. 3 to 35.

In the polyamine compound having an acid group-containing side chain of the fifth form, the number of moles of the unsubstituted polyamine compound used to form the polyamine compound having an acid group-containing side chain and the acid group-containing side chain are formed. Therefore, the ratio of the acid group-containing compound used for the purpose is preferably 75 to 3/25 to 97. More preferably, it is 50-3 / 50-97, More preferably, it is 30-4 / 70-96, Most preferably, it is 25-5 / 75-95.

The polyamine compound of the fifth form may have other side chains other than the acid group-containing side chains. Examples of other side chains include hydrocarbon group-containing side chains, oxyalkylene group-containing side chains, and the like.
The hydrocarbon group-containing side chain can be formed by reacting a compound having a structure in which a hydrocarbon group is bonded to an atomic group that reacts with an amino group, with a polyamine compound.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, and may have any of a linear, branched, or cyclic structure. More preferably, it is a 4-30 hydrocarbon group. The hydrocarbon group is preferably a linear, branched or cyclic alkyl group or aryl group.
As an atomic group (group) that reacts with an amino group, a carboxyl group, a group derived from a carboxylic anhydride; a group derived from (meth) acrylic acid; a glycidyl ether group; an epoxy group; an isocyanate group; a thioisocyanate group; Hydroxy group; halogen atom and the like.
The compound having a structure in which a hydrocarbon group is bonded to a group derived from (meth) acrylic acid is a (meth) acrylic acid ester.

Specific examples of compounds having a structure in which a hydrocarbon group is bonded to an atomic group that reacts with the amino group include glycidyl ethers of higher alcohols such as octyl glycidyl ether, lauryl glycidyl ether, stearyl glycidyl ether, and 2-ethylhexyl glycidyl ether; Glycidyl ethers of alkylphenols such as octylphenyl glycidyl ether, nonylphenyl glycidyl ether, laurylphenyl glycidyl ether, stearylphenyl glycidyl ether; octylcyclopentyl glycidyl ether, octylcyclohexyl glycidyl ether, nonylcyclopentyl glycidyl ether, nonylcyclohexyl glycidyl ether, laurylcyclopentylglycidyl Ether, lauryl cyclohexyl Glycidyl ethers of alkylcycloalkanols such as sidyl ether, stearylcyclopentyl glycidyl ether, stearyl cyclohexyl glycidyl ether; glycidyl ethers of alkyl benzyl alcohol such as octyl benzyl glycidyl ether, nonyl benzyl glycidyl ether, lauryl benzyl glycidyl ether, stearyl benzyl glycidyl ether Epoxy hexane, α-olefin epoxide which is a mixture having 12 to 14 carbon atoms, α-olefin epoxide which is a mixture having 16 to 18 carbon atoms, α-olefin epoxide which is a mixture having 20 to 28 carbon atoms, 30 or more carbon atoms 1,2-epoxyalkanes such as α-olefin epoxides, which are mixtures of: octyl isocyanate, decyl isocyanate Alkyl isocyanates such as octanol, octadecyl isocyanate; monoisocyanate compounds obtained by reaction of alcohols such as octanol, lauryl alcohol, stearyl alcohol and diisocyanates such as tolylene diisocyanate; octanol, lauryl alcohol, stearyl alcohol, etc. Halides in which the terminal hydroxyl groups of alcohols are substituted with halogen atoms such as chlorine, bromine and iodine; saturated fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid; oleic acid, linoleic acid, linolenic acid and eleostearin Unsaturated fatty acids such as acids; butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) a Acrylic acid myristyl, and the like (meth) acrylic acid esters such as stearyl (meth) acrylate. These compounds may be used alone or in combination of two or more. When two or more compounds are used, at least one of them is an epoxy group, an isocyanate group, a thioisocyanate group, an aldehyde. A compound having a functional group selected from the group consisting of a group, a halogenated alkyl group and an acyl halide group is preferred.

The amount of the compound having a structure in which a hydrocarbon group is bonded to an atomic group that reacts with the amino group is preferably 0.01 to 0.90 mole per active amine hydrogen of the unsubstituted polyamine compound. . More preferably, it is 0.05-0.90 mol, More preferably, it is 0.10-0.85 mol, Most preferably, it is 0.17-0.80 mol, Most preferably, it is 0 .23 to 0.80 mol.

The above oxyalkylene group-containing side chain is obtained by adding a polyamine compound with (poly) alkylene oxide or a compound having an alkoxy group at one end of (poly) alkylene oxide, or reacting an amino group with (poly) alkylene oxide. It can be formed by reacting a compound to which an atomic group is bonded. Examples of the atomic group that reacts with the amino group include the same atomic groups as described above.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, and octylene oxide. 8 alkylene oxides. Among these, C2-C4 alkylene oxide is preferable.
One type of alkylene oxide may be used, or two or more types may be used in combination.

Examples of the compound in which an atomic group that reacts with an amino group is bonded to the (poly) alkylene oxide include methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, methoxy ( Examples thereof include poly) ethylene glycol maleate and methoxy (poly) ethylene glycol (poly) propylene glycol maleate. These may use 1 type and may use 2 or more types together.

When the polyamine compound has an oxyalkylene group-containing side chain, the average number of added moles of oxyalkylene groups per oxyalkylene group-containing side chain is preferably 1 to 500. More preferably, it is 1-300, More preferably, it is 1-100.

When the polyamine compound has an oxyalkylene group-containing side chain, the oxyalkylene group-containing side chain is preferably bonded to 10 to 100% of the nitrogen atoms of the polyamine compound. More preferably, it is 30 to 100%, and still more preferably 50 to 100%.

The reaction conditions for reacting the compound for introducing a side chain with the unsubstituted polyamine compound are not particularly limited as long as the reaction proceeds, but the reaction temperature is preferably 50 to 150 ° C. The reaction time is preferably 1 to 100 hours.

The solvent used for the reaction between the unsubstituted polyamine compound and the compound for introducing a side chain is not particularly limited as long as the reaction proceeds, but water, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutyl. Alcohols such as alcohol and isoamyl alcohol; hydrocarbons such as n-butane, propane, benzene, cyclohexane and naphthalene; esters such as methyl acetate, ethyl acetate, ethyl benzoate and ethyl lactate; (poly) ethylene glycol, ethylene Examples include polyhydric alcohols such as glycol monobutyl ether, ethylene glycol monobutyl ether acetate, tetraethylene glycol, (poly) propylene glycol, propylene glycol monobutyl ether and derivatives thereof. Is, water, alcohol, hydrocarbon, and preferably an ester, especially water, methanol, ethanol, isopropanol, cyclohexane, ethylene glycol, ethylene glycol monobutyl ether, ethyl acetate is preferred.

The reaction between the unsubstituted polyamine compound and the compound for introducing a side chain may use a catalyst in order to accelerate the reaction. A titanium-based catalyst such as tetrabutyl titanate or tetraisopropyl titanate; Tin-based catalysts such as tin, tin octylate and monobutyltin oxide; acids such as p-toluenesulfonic acid and the like can be used.
For other reaction conditions, Japanese Patent No. 4436921 and Japanese Patent Application Laid-Open No. 2008-230865 can be referred to.

It is preferable that at least one compound selected from the group consisting of (I) to (V) contained in the shrinkage reducing agent for hydraulic material satisfies the following condition (1).
(1) 15-stroke flow 10 minutes after the start of kneading between a mortar composition based on JASS 5 M402 to which the compound is added at a solid content concentration of 0.1% and a mortar based on JASS 5 M402 not containing the compound Ratio of values: (15 striking flow value of the compound-containing mortar composition) / (15 striking flow value of the mortar not containing the compound) × 100 is 120 or less The condition (1) is that the compound has a mortar composition Means that the flow value of the object is not too high. When the compound contained in the shrinkage reducing agent for hydraulic material has such a predetermined dispersion performance, the shrinkage reduction performance is improved.
In addition, the mortar based on JASS 5 M402 is described in Examples described later.

If the ratio of the 15 shot flow value of the mortar composition containing the compound (1) at a solid content concentration of 0.1% to the 15 shot flow value of the mortar not containing the compound is 120 or less, the compound Although the performance to improve the flow value is not too high, the ratio is more preferably 118 or less. More preferably, it is 115 or less. Further, the ratio is more preferably 90 or more, further preferably 95 or more, and particularly preferably 97 or more.

It is preferable that at least one compound selected from the group consisting of (I) to (V) included in the shrinkage reducing agent for hydraulic material also satisfies the following condition (2).
(2) 15-stroke flow value 2 hours after the start of kneading of the mortar composition according to JASS 5 M402 to which the compound was added at a solid content concentration of 0.1% with respect to the mortar according to JASS 5 M402 not containing the compound And the ratio of 15 stroke flow values after 10 minutes from the start of kneading: (ratio of 15 stroke flow values after 2 hours) / (ratio of 15 stroke flow values after 10 minutes) × 100 is 110 The condition (2) below means that the performance of the compound to improve the flow retention of the mortar composition is not too high. When the compound contained in the shrinkage reducing agent for hydraulic material has such a predetermined dispersion performance, the shrinkage reduction performance is improved.

The ratio of the flow value at 15 strokes after 2 hours from the start of kneading of the mortar composition containing the compound at a solid content concentration of 0.1% with respect to the mortar not containing the compound of (2), that is, (containing the compound The ratio of the value of the 15 stroke flow value after 2 hours of the mortar composition) / (15 stroke flow value after 2 hours of the mortar not containing the compound) and the 15 stroke flow value after 10 minutes from the start of kneading, The ratio of the value of (15 stroke flow value after 10 minutes of the compound-containing mortar composition) / (15 stroke flow value after 10 minutes of the mortar not containing the compound) × 100 is 110 or less. The compound does not have too high performance for improving the flow retention, but the ratio is more preferably 109 or less. More preferably, it is 105 or less. Further, the ratio is more preferably 85 or more, further preferably 90 or more, and particularly preferably 95 or more.

(Polycarboxylic acid water reducing agent)
The polycarboxylic acid water reducing agent contained in the admixture composition of the present invention is derived from the structural unit (a) derived from the unsaturated carboxylic acid monomer (A) and the unsaturated polyalkylene glycol monomer (B). And a copolymer having a structural unit (b) (hereinafter also referred to as a polycarboxylic acid copolymer).

The unsaturated carboxylic acid monomer (A) (hereinafter also referred to as monomer (A)) comprises an unsaturated double bond (carbon-carbon double bond), a carboxy group and / or a carboxylate group. If it is a monomer containing, it will not be restrict | limited in particular.

Here, including a carboxy group and / or a carboxylate group means that a group represented by —COOM (M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group) is 1 per molecule. It means having more than one. Examples of metal atoms include alkali metals such as sodium, lithium, potassium, rubidium and cesium; alkaline earth metals such as magnesium, calcium, strontium and barium; aluminum and iron. Organic amine groups include monoethanolamine groups, diethanolamine groups, triethanolamine groups and other alkanolamine groups; monoethylamine groups, diethylamine groups, triethylamine groups and other alkylamine groups; ethylenediamine groups, triethylenediamine groups and other polyamines Groups and the like. Among these, the carboxylate group is more preferably an ammonium salt, a sodium salt or a potassium salt, and still more preferably a sodium salt.

As the unsaturated carboxylic acid monomer (A), the unsaturated monocarboxylic acid monomer having one carboxy group (or carboxylic acid base) in one molecule includes acrylic acid, methacrylic acid, and crotonic acid. And these metal salts, ammonium salts, organic amine salts (organic ammonium salts); unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and alcohols having 1 to 30 carbon atoms Half ester; half amide of the above unsaturated dicarboxylic acid and amine having 1 to 30 carbon atoms; alkyl (poly) alkylene glycol obtained by adding 1 to 300 mol of alkylene oxide having 2 to 18 carbon atoms to the above alcohol or amine Half ester of said unsaturated dicarboxylic acids with said unsaturated dicarboxylic acids and 2-1 carbon atoms Glycol or half ester and the like of polyalkylene glycol of molar number of addition 2-300 of these glycols.
Examples of unsaturated dicarboxylic acid monomers having two carboxy groups (or carboxylate groups) in one molecule include maleic acid, itaconic acid, citraconic acid, fumaric acid, or metal salts, ammonium salts, organic amines thereof. Salts (organic ammonium salts) and the like, and examples of these anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
As the unsaturated carboxylic acid monomer, an unsaturated monocarboxylic acid monomer is preferable. More preferred is acrylic acid or methacrylic acid.

The unsaturated polyalkylene glycol monomer (B) (hereinafter also referred to as monomer (B)) is represented by the following formula (20);

(In formula, R <^26> , R <^27> and R <^28> are the same or different and represent a hydrogen atom or a methyl group. R < ²⁹ > represents a hydrogen atom or a C1-C30 hydrocarbon group. (R ³⁰ O) is the same or different and represents an oxyalkylene group, s represents the average number of added moles of the oxyalkylene group, and is a number from 1 to 500. y represents a number from 0 to 2. Z is preferably a compound represented by 0 or 1.

In the above formula (20), the number of carbon atoms of R ³⁰ in the oxyalkylene group R ³⁰ O is suitably 2-18, preferably 2-8, and more preferably 2-4. Further, any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like can be used in any of random addition, block addition, alternating addition, and the like. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable to include an oxyethylene group as an essential component in the oxyalkylene group, more preferably 50 mol% or more is an oxyethylene group, and 90 mol% or more. More preferably, it is an oxyethylene group.

In the above formula (20), the average added mole number s of the oxyalkylene group is suitably 1 to 500. As the average added mole number is larger, the hydrophilicity of the resulting polymer tends to be improved and the dispersion performance tends to be improved. If the average added mole number is 500 or less, it is possible to suppress a decrease in copolymerization reactivity. The average added mole number s is preferably 2 to 500, more preferably 5 to 500, still more preferably 10 to 500, particularly preferably 15 to 500, and most preferably 20 to 300.

In the above formula (20), R ²⁶ , R ²⁷ and R ²⁸ are the same or different and are a hydrogen atom or a methyl group. Preferably, R ²⁶ and R ²⁷ are hydrogen atoms, and R ²⁸ is a hydrogen atom or a methyl group.

In the above formula (20), R ²⁹ may be a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group having 1 to 30 carbon atoms has a radical polymerizable unsaturated bond. Those having 1 to 30 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), phenyl groups having 6 to 30 carbon atoms, alkylphenyl groups, phenylalkyl groups, (alkyl) phenyl groups. in substituted phenyl groups include, an aromatic group having a benzene ring such as a naphthyl group are preferred, hydrophobicity increases as the number of carbon atoms of the hydrocarbon group is increased, since the dispersibility decreases, R ²⁹ In the case where is a hydrocarbon group, the number of carbon atoms is preferably 1 to 22, more preferably 1 to 18, still more preferably 1 to 12, and particularly preferably 1 to 4. R ²⁹ is most preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

In the above formula (20), y represents a number from 0 to 2, and z represents 0 or 1. When z is 0, the monomer (B) is an ether monomer. In this case, y is preferably 2. In this case, R ²⁸ is more preferably a methyl group.
When z is 1, the monomer (B) is an ester monomer, and y is preferably 0 in this case. In this case, R ²⁸ is more preferably a hydrogen atom or a methyl group, and still more preferably R ²⁸ is a methyl group.
As the monomer (B), compounds in which z in the above formula (20) is 0 and R ²⁹ is a hydrogen atom include (poly) ethylene glycol allyl ether, (poly) ethylene glycol methallyl ether, (poly ) Ethylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol methallyl ether, (poly) ethylene (poly) propylene glycol 3-methyl- 3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly) ethylene (poly) butylene glycol methallyl ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, etc. Can be mentioned.

As the monomer (B), compounds in which z in the above formula (20) is 0 and R ²⁹ is a hydrocarbon group having 1 to 30 carbon atoms include methoxy (poly) ethylene glycol allyl ether, methoxy (Poly) ethylene glycol methallyl ether, methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) propylene glycol methallyl ether, Methoxy (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) butylene glycol allyl ether, methoxy (poly) ethylene (poly) butylene glycol methallyl ether, methoxy (poly) D Examples include tylene (poly) butylene glycol 3-methyl-3-butenyl ether.

As the monomer (B), compounds in which z in the above formula (20) is 1 and R ²⁹ is a hydrogen atom include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol polybutylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meta) ) Acrylate, polyethylene glycol polypropylene glycol polybutylene glycol (poly) alkylene glycol (meth) ) Acrylates.

As the monomer (B), compounds in which z in the above formula (20) is 1 and R ²⁹ is a hydrocarbon group having 1 to 30 carbon atoms include methoxypolyethylene glycol mono (meth) acrylate, methoxy Polypropylene glycol mono (meth) acrylate, methoxypolybutylene glycol mono (meth) acrylate, methoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol polybutylene glycol mono (meth) acrylate, methoxypolypropylene glycol polybutylene glycol mono (meta) ) Acrylate, methoxy polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono ( (Meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, ethoxypolybutylene glycol mono (meth) acrylate, ethoxypolyethyleneglycolpolypropyleneglycol mono (meth) acrylate, ethoxypolyethyleneglycolpolybutyleneglycolmono (meth) acrylate, ethoxypolypropyleneglycolpoly Examples include alkoxy polyalkylene glycol (meth) acrylates having 1 to 30 carbon atoms in the alkoxy group, such as butylene glycol mono (meth) acrylate and ethoxy polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate.

The unsaturated (poly) alkylene glycol monomer (B) is preferably (poly) ethylene glycol 3-methyl-3-butenyl ether or methoxypolyethylene glycol mono (meth) acrylate.

As long as the copolymer contained in the polycarboxylic acid-based water reducing agent has the structural units (a) and (b), other monomers other than the monomers (A) and (B) ( It may have a structural unit derived from C). The other monomer (C) is not particularly limited as long as it is copolymerizable with the monomers (A) and (B). For example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid Diesters of unsaturated dicarboxylic acids and alcohols having 1 to 30 carbon atoms; diamides of unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; and alcohols and amines having 2 to 18 carbon atoms Diesters of an alkyl (poly) alkylene glycol to which 1 to 300 moles of an alkylene oxide are added and the above unsaturated dicarboxylic acids; the above unsaturated dicarboxylic acids and a glycol having 2 to 18 carbon atoms or the number of moles of these glycols added Diesters with 2 to 300 polyalkylene glycols; methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate, and other esters of unsaturated monocarboxylic acids and alcohols having 1 to 30 carbon atoms; Half amides of glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 addition moles of these glycols

(Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate, etc. Di (meth) acrylates; polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; triethylene glycol dimaleate, polyethylene glycol (Poly) alkylene glycol dimaleates such as dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acrylate Xylpropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- ( Unsaturated sulfonic acids such as (meth) acryloxybutyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid, and monovalents thereof Metal salts, divalent metal salts, ammonium salts and organic amine salts (organic ammonium salts); Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; Styrene, α -Methyl Vinyl aromatics such as styrene, vinyltoluene, p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) Alkanediol mono (meth) acrylates such as acrylate; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene

Unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, Unsaturated amines such as dibutylaminoethyl acrylate and vinyl pyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth) allyl ether, etc. Allyls; polydimethyl Roxanpropylaminomaleamic acid, polydimethylsiloxane aminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane -(1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1- And siloxane derivatives such as propyl-3-methacrylate).

In the polycarboxylic acid copolymer, the content ratio of the structural unit (a) is preferably 7 to 50% by mass with respect to 100% by mass of all the structural units. More preferably, it is 10-45 mass%, More preferably, it is 12-30 mass%.
In the polycarboxylic acid copolymer, the content ratio of the structural unit (b) is preferably 50 to 93% by mass with respect to 100% by mass of all the structural units. More preferably, it is 55-90 mass%, More preferably, it is 70-88 mass%.
When the proportion of the structural units (a) and / or (b) in the polycarboxylic acid copolymer is within the above preferable range, the dispersion performance of the copolymer is further improved.

In the polycarboxylic acid copolymer, the proportion of the structural unit (c) in the copolymer is preferably 0 to 50% by mass with respect to 100% by mass of all structural units. More preferably, it is 0-30 mass%, More preferably, it is 0-20 mass%.

The polycarboxylic acid copolymer preferably has a weight average molecular weight of 1,000 to 1,000,000. More preferably, it is 2500 to 500,000, and when the weight average molecular weight is 2500 to 500,000, the water reducing performance and slump loss preventing ability of the copolymer can be made more satisfactory. More preferably, it is 5000-250,000, More preferably, it is 10,000-100000. In addition, the weight average molecular weight of the said polycarboxylic acid-type copolymer can be measured on the measurement conditions as described in an Example by GPC.

Although the production of the polycarboxylic acid copolymer is not particularly limited, it can be produced by polymerizing the monomer component, and specific examples and preferred examples of the monomer component are as described above. Moreover, the content ratio of the monomers (A), (B) and (C) with respect to 100% by mass of the monomer component is the structural units (a), (b) and (c) with respect to 100% by mass of all the structural units described above. ).

A chain transfer agent is usually used in the polymerization reaction for obtaining a polymer. Examples of the chain transfer agent include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; secondary alcohols such as isopropyl alcohol; Phosphoric acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite and salts thereof (sodium sulfite, sodium hydrogen sulfite, sulfite And hydrophilic chain transfer agents such as lower oxides of sodium dithionate, sodium metabisulfite and the like and salts thereof.

A hydrophobic chain transfer agent can also be used as the chain transfer agent. Examples of the hydrophobic chain transfer agent include 3 carbon atoms such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, and octyl 3-mercaptopropionate. A thiol chain transfer agent having the above hydrocarbon group is preferably used.

The amount of the chain transfer agent used may be appropriately set, but is preferably 0.5 to 5.0 mol, more preferably 1.0 to 4.0, with respect to 100 mol of the total amount of monomer components. It is mol%, More preferably, it is 1.5-3.0 mol%.

The polymerization reaction can be performed by a method such as solution polymerization or bulk polymerization using a radical polymerization initiator as necessary. The solution polymerization can be performed batchwise, continuously, or a combination thereof. Examples of the solvent used in this case include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; benzene, toluene, Aromatic or aliphatic hydrocarbons such as xylene, cyclohexane and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, it is preferable to perform polymerization by an aqueous solution polymerization method.

Among the above solution polymerizations, in aqueous solution polymerization, it is preferable to use a water-soluble radical polymerization initiator because it is not necessary to remove insoluble components after polymerization. For example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azoamidine compounds such as 2,2′-azobis-2-methylpropionamidine hydrochloride, 2,2′-azobis-2- Cyclic azoamidine compounds such as (2-imidazolin-2-yl) propane hydrochloride, azonitrile compounds such as 2-carbamoylazoisobutyronitrile, 2,4′-azobis {2-methyl-N- [2- (1- Water-soluble azo initiators such as azoamide compounds such as (hydroxybutyl)] propionamide}, macroazo compounds such as esters of 4,4′-azobis (4-cyanovaleric acid) and (alkoxy) polyethylene glycol, These 1 type (s) or 2 or more types can be used. Among these, hydrogen peroxide and a persulfuric acid initiator are preferable.

The amount of the radical polymerization initiator used is preferably 0.01 to 10.0 mol, more preferably 0.01 to 10.0 mol, and still more preferably with respect to 100 mol of the total amount of monomer components. Is 0.05 to 8.0 mol, particularly preferably 0.1 to 7.0 mol.

When using the above radical polymerization initiator, alkali metal sulfite such as sodium hydrogen sulfite, metabisulfite, sodium hypophosphite, Fe (II) salt such as molle salt, sodium hydroxymethanesulfinate dihydrate, Accelerators (reducing agents) such as hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination. For example, a combination of hydrogen peroxide and an organic reducing agent is possible. Examples of the organic reducing agent include L-ascorbic acid (salt), L-ascorbic acid ester, erythorbic acid (salt), erythorbic acid ester, and the like. It can be used suitably. These radical polymerization initiators and accelerators (reducing agents) may be used alone or in combination of two or more.
The amount of the accelerator (reducing agent) used is not particularly limited. For example, when the total amount of the polymerization initiator used in combination is 100 mol, it is preferably 10 mol or more, more preferably 20 mol or more. More preferably, it is 50 mol or more, preferably 1000 mol or less, more preferably 500 mol or less, still more preferably 400 mol or less.

In the above polymerization reaction, the polymerization conditions such as the polymerization temperature are appropriately determined depending on the polymerization method used, the solvent, the polymerization initiator, and the chain transfer agent, but the polymerization temperature is preferably 0 ° C. or higher, It is preferable that it is 150 degrees C or less. More preferably, it is 30 degreeC or more, More preferably, it is 50 degreeC or more. More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less.

The proportion of the shrinkage reducing agent for hydraulic material contained in the admixture composition of the present invention is preferably 10 to 99.9 mass% with respect to 100 mass% of the admixture composition. More preferably, it is 20-95 mass%, More preferably, it is 30-90 mass%.

The proportion of the polycarboxylic acid-based water reducing agent contained in the admixture composition of the present invention is preferably 0.1 to 90 mass% with respect to 100 mass% of the admixture composition. More preferably, it is 5-80 mass%, More preferably, it is 10-70 mass%.

The admixture composition of the present invention can be suitably used as a cement additive. The cement additive containing the admixture composition of the present invention has the effect of reducing shrinkage that occurs when the hydraulic material dries, reducing or preventing cracks in the cured product, improving fillability, and reducing warping. It can be used mainly for prevention, prevention of peeling, and the like, and can be suitably used for a hydraulic material described later.
In addition to the shrinkage reducing agent for hydraulic material and the polycarboxylic acid-based water reducing agent, the admixture composition may contain other components as necessary.
As other components, those similar to those described in JP-A-2002-293596 can be used.

（式（１）中、Ｒ^１〜Ｒ^３は、同一又は異なって、水素原子又はメチル基を表す。Ｒ^４Ｏは、同一又は異なって、炭素数２〜１８のオキシアルキレン基を表す。Ｒ^５は、水素原子又は炭素数１〜３０の炭化水素基を表す。ｐは、０〜５の数を表し、ｑは、０又は１の数である。ｎは、オキシアルキレン基の平均付加モル数を表し、７〜３００の数である。）で表される構造単位（Ｉ）と、下記式（２）；

（式（２）中、Ｒ^６〜Ｒ^８は、同一又は異なって、水素原子、メチル基又は−（ＣＨ_２）_ｍＣＯＯＺ’基を表す。ここで、ｍは、０〜２の整数であり、Ｚ’は、水素原子、金属原子、アンモニウム基、有機アミン基又は炭化水素基を表す。Ｚは、水素原子、金属原子、アンモニウム基又は有機アミン基を表す。）で表される構造単位（ＩＩ）とを有する重合体であって、該重合体は、構造単位（Ｉ）の割合が、全構造単位１００質量％に対して、７０〜９７質量％であり、構造単位（ＩＩ）の割合が、全構造単位１００モル％に対して、１０〜５９モル％である重合体
（ＩＩ）：
下記式（３）；
［Ｖ−（ＯＡ^１）_ｆ−］_ｋＹ［−（Ｂ^１Ｏ）_ｇ−Ｗ］_ｌ （３）
（式（３）中、Ｖ、Ｗは、同一又は異なって、水素原子又は炭素原子数１〜３０の炭化水素基を表す。ＯＡ^１、Ｂ^１Ｏは、同一又は異なって、炭素数２〜１８のオキシアルキレン基を表す。ｆ、ｇは、それぞれ、ＯＡ^１、Ｂ^１Ｏの平均付加モル数を表し、ｆ、ｇは、同一又は異なって、０〜２０００であり、ｆ＋ｇ＝１〜２０００である。Ｙは活性水素を有する化合物の残基を表す。ｋ、ｌは、同一又は異なって、０〜６である。ただし、ｋ＋ｌは１以上である。）で表されるポリエーテル化合物にエチレン性不飽和単量体をグラフト重合してなる重合体であって、該エチレン性不飽和単量体は不飽和カルボン酸系単量体を含み、該重合体は、不飽和カルボン酸系単量体由来の構造単位の割合が、全構造単位１００質量％に対して、０．１〜１２質量％であり、該ポリエーテル化合物の重量平均分子量が、１５００〜５００００である重合体
（ＩＩＩ）：
エチレン性不飽和単量体成分由来の高分子鎖（Ａ）と（ポリ）アルキレングリコール鎖（Ｂ）の末端とが結合部位（Ｘ）を介して結合した構造を有する共重合体であって、該エチレン性不飽和単量体は、不飽和アニオン系単量体を含み、該共重合体は、不飽和アニオン系単量体由来の構造単位の割合が、（ポリ）アルキレングリコール鎖１モルに対して１〜３０モルであり、（ポリ）アルキレングリコール鎖を形成する（ポリ）アルキレングリコールの重量平均分子量が、１５００〜５００００である（ポリ）アルキレングリコール系ブロック共重合体
（ＩＶ）：
直鎖状又は分岐状ポリアルキレングリコール鎖の少なくとも２つの末端に、金属、金属化合物及び金属イオンの少なくとも１つに対して吸着能を示す有機残基が結合したポリアルキレングリコール化合物であって、該ポリアルキレングリコール化合物は、ポリアルキレングリコール鎖を形成するポリアルキレングリコールの重量平均分子量が、１５００〜５００００であり、該有機残基は、カルボニル基、水酸基、アミノ基、チオール基、リン酸基、亜リン酸基及びシラン基からなる群より選択される少なくとも１つの官能基を有するポリアルキレングリコール化合物
（Ｖ）：
酸基含有側鎖を有するポリアミン化合物であって、該ポリアミン化合物は、未置換ポリアミン化合物由来の構造単位と不飽和カルボン酸系単量体由来の構造単位とを有し、該不飽和カルボン酸系単量体由来の構造単位の割合が、全構造単位１００モル％に対して、２５〜９９モル％である酸基含有側鎖を有するポリアミン化合物 <Hydraulic material composition>
The present invention is also a hydraulic material composition comprising a shrinkage reducing agent for hydraulic material, a polycarboxylic acid-based water reducing agent, and a hydraulic material, wherein the shrinkage reducing agent for hydraulic material includes the following (I) to ( It is also a hydraulic material composition comprising at least one compound selected from the group consisting of V).
(I):
Following formula (1);

(In Formula (1), R < ¹ > -R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R < ⁴ > O is the same or different and represents a C2-C18 oxyalkylene group. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, p represents a number of 0 to 5, q represents a number of 0 or 1. n represents an average addition mole of an oxyalkylene group. A structural unit (I) represented by the following formula (2):

(In the formula ^(2), R 6 ~R ⁸ are the same or different, a hydrogen atom, a methyl group or a _-. (Representing _CH 2) m COOZ 'group wherein, m is an integer from 0 to 2 , Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group, and Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). II), wherein the proportion of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of all the structural units, and the proportion of the structural unit (II) However, the polymer (II) is 10 to 59 mol% with respect to 100 mol% of all structural units:
Following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In Formula (3), V and W are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. OA ¹ and B ¹ O are the same or different and have 2 to 2 carbon atoms. 18 represents an oxyalkylene group, and f and g represent the average number of added moles of OA ¹ and B ¹ O, respectively, and f and g are the same or different and are 0 to 2000, and f + g = 1 to 2000. Y represents a residue of a compound having active hydrogen, and k and l are the same or different and are 0 to 6. However, k + 1 is 1 or more. A polymer obtained by graft polymerization of an ethylenically unsaturated monomer, the ethylenically unsaturated monomer containing an unsaturated carboxylic acid monomer, and the polymer comprising an unsaturated carboxylic acid monomer The proportion of the structural unit derived from the monomer is 0 with respect to 100% by mass of all the structural units. 1 to 12 wt%, weight average molecular weight of the polyether compound is a 1,500 to 50,000 polymer (III):
A copolymer having a structure in which a polymer chain derived from an ethylenically unsaturated monomer component (A) and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X), The ethylenically unsaturated monomer includes an unsaturated anionic monomer, and the copolymer has a ratio of structural units derived from the unsaturated anionic monomer to 1 mol of the (poly) alkylene glycol chain. The (poly) alkylene glycol block copolymer (IV) having a weight average molecular weight of 1 to 30 moles and the weight average molecular weight of the (poly) alkylene glycol forming the (poly) alkylene glycol chain is 1500 to 50000:
A polyalkylene glycol compound in which an organic residue capable of adsorbing at least one of a metal, a metal compound, and a metal ion is bonded to at least two ends of a linear or branched polyalkylene glycol chain, In the polyalkylene glycol compound, the polyalkylene glycol forming the polyalkylene glycol chain has a weight average molecular weight of 1500 to 50000, and the organic residue includes a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphate group, Polyalkylene glycol compound (V) having at least one functional group selected from the group consisting of a phosphate group and a silane group:
A polyamine compound having an acid group-containing side chain, the polyamine compound having a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid monomer, the unsaturated carboxylic acid type A polyamine compound having an acid group-containing side chain in which the proportion of structural units derived from monomers is 25 to 99 mol% with respect to 100 mol% of all structural units

The shrinkage reducing agent for hydraulic material and the polycarboxylic acid-based water reducing agent contained in the hydraulic material composition are the same as the shrinkage reducing agent for hydraulic material and the polycarboxylic acid-based water reducing agent in the above-mentioned admixture composition. It is preferable that
Moreover, it is preferable that the said hydraulic material composition contains water further.

The method for producing a shrinkage reducing agent for hydraulic material, a polycarboxylic acid-based water reducing agent, a hydraulic material and water of the present invention is not particularly limited, and the shrinkage reducing agent for hydraulic material of the present invention, polycarboxylic acid A method of adding and mixing the water reducing agent, hydraulic material and water by various commonly used techniques described in JP-T-2008-503432, JP-T-2008-512268, etc. can be used. Examples of methods that are usually used include the following methods, and two or more of these may be used in combination.
(A) A method for producing a hydraulic material composition by diluting a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent with water and mixing it with a hydraulic material. (B) A shrinkage reducing agent and a polycarboxylic acid-based water reducing agent. (C) A method for producing a hydraulic material composition by adding water to a hydraulic material after being powdered and adding water to the resulting mixture (c) A shrinkage reducing agent and a polycarboxylic acid-based water reducing agent are added at the time of hydraulic material production. A method of adding a hydraulic material containing a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent and then adding water to produce a hydraulic material composition (d) In the method of (c) above, As a method of adding a shrinkage reducing agent at the time of manufacturing a hard material, a method of adding a shrinkage reducing agent at the same time as a grinding aid or a grinding aid (when the hydraulic material is cement)
(E) A method of spraying and adding an aqueous solution containing a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent during transportation after producing a hydraulic material

The hydraulic material in which the shrinkage reducing agent for hydraulic material and the polycarboxylic acid-based water reducing agent of the present invention are used is not particularly limited as long as it has hydraulic property or latent hydraulic property. For example, ordinary Portland cement, Portland cement such as early-strength Portland cement, moderately hot Portland cement, low-heat Portland cement, silica cement, fly ash cement, blast furnace cement, alumina cement, cement containing high belite, various mixed cements: tricalcium silicate, dicalcium silicate, Constituent components of cement such as tricalcium aluminate and tetracalcium iron aluminate; fly ash having latent hydraulic properties and the like. These may be used alone or in combination of two or more. Among these, ordinary portland cement is usually used and can be suitably applied.

As a usage-amount of the shrinkage reducing agent for hydraulic materials in the hydraulic material composition of this invention, it is preferable that it is 0.0001 to 10 weight% in conversion of solid content with respect to a hydraulic material, for example. If it is less than 0.0001% by weight, the shrinkage reduction performance may not be sufficient, and if it exceeds 10% by weight, there is a risk that a delay in curing of the hydraulic material is likely to occur. More preferably, it is 0.001 to 5 weight%, More preferably, it is 0.005 to 3 weight%, Most preferably, it is 0.01 to 1 weight%.

As usage-amount of the polycarboxylic acid type water reducing agent in the hydraulic material composition of this invention, it is preferable that it is 0.001 to 10 weight% in conversion of solid content with respect to a hydraulic material, for example. More preferably, it is 0.01-5 weight%, More preferably, it is 0.05-3 weight%.

The mixing ratio of the shrinkage reducing agent and the polycarboxylic acid-based water reducing agent (mass of shrinkage reducing agent) / (mass of water reducing agent) in the hydraulic material composition is 99.9 / 0.1 to 40/60. Preferably there is. More preferably, it is 99/1 to 50/50, still more preferably 98/2 to 60/40, particularly preferably 98/2 to 65/35, and most preferably 97/3 to 3. 70/30.

The mixing ratio of water in the hydraulic material composition is not particularly limited, and is preferably 10 to 80% by weight with respect to cement, for example. If it is less than 10% by weight, the mixing of various components may be insufficient and molding may not be possible or the strength may be reduced. If it exceeds 80% by weight, the strength of the cured product of the hydraulic material composition may be reduced. May decrease. More preferably, it is 15-75 weight%, More preferably, it is 20-70 weight%, Most preferably, it is 25-65 weight%.

When using the hydraulic material composition as mortar or concrete, as sand and stone blended in the hydraulic material composition, those used in conventionally known cement compositions can be used, not particularly limited, for example, Natural fine aggregates such as river sand, sea sand and mountain sand made from rocks by natural action; artificial fine aggregates obtained by pulverizing these rocks and slabs; lightweight fine aggregates and the like. About the compounding quantity of sand, what is necessary is just to be the same as that of a conventionally well-known cement composition, and it does not specifically limit. Further, the blending amount of the stone may be the same as that of the conventionally known cement composition, and is not particularly limited. For example, the fine aggregate ratio is preferably 20 to 60% by volume. When the content is less than 20% by volume, the concrete becomes loose, and in a concrete having a large slump, the coarse aggregate and the mortar content may be easily separated. If it exceeds 60% by volume, a large amount of unit cement and unit water are required, and there is a risk that the concrete will have poor fluidity. More preferably, it is 30-50 volume%.

Other materials may be blended in the hydraulic material composition as necessary. As other materials, the same materials as conventionally known cement compositions can be used, and are not particularly limited. For example, other water reducing agents other than the polycarboxylic acid-based water reducing agent, AE agent (air entraining agent) , Antifoaming agents, curing accelerators, retarders, rust inhibitors, expanding materials, silica powder, and fiber materials such as steel fibers and glass fibers. The blending amounts of these materials may be the same as those of conventionally known hydraulic material compositions, and are not particularly limited.

When the said hydraulic material composition contains another water reducing agent, it is preferable that content of other water reducing agents is 0.001-10 weight part in conversion of solid content with respect to 100 weight part of hydraulic material. . More preferably, it is 0.01-5 weight part, More preferably, it is 0.1-3 weight part.

The other water reducing agent contained in the hydraulic material composition of the present invention is not particularly limited as long as it functions as a water reducing agent. For example, monovalent metal salts, divalent metal salts, ammonium salts of lignin sulfonic acid, Examples include lignin sulfonates such as organic amine salts; polyol derivatives; naphthalene sulfonic acid formalin condensates. Among these water reducing agents, lignin sulfonate is preferable.

From the point of making the hydraulic material composition of the present invention excellent in freeze-thaw resistance, it is preferable that fine bubbles are contained in the hydraulic material composition, and an air entraining agent (AE agent) is included. preferable.
When the hydraulic material composition of this invention contains AE agent, it is preferable that content of AE agent is 0.002 weight part or more with respect to 100 weight part of hydraulic materials. By including in such a ratio, the performance of the AE agent such as improvement in freeze-thaw resistance can be effectively exhibited. The content of the AE agent is more preferably 0.0025 parts by weight or more, further preferably 0.003 parts by weight or more, and particularly preferably 0.004 parts by weight with respect to 100 parts by weight of the hydraulic material. It is more than part by weight. Moreover, it is preferable that content of AE agent is 0.1 weight part or less with respect to 100 weight part of hydraulic materials normally. More preferably, it is 0.05 parts by weight or less, and still more preferably 0.04 parts by weight or less.

When the hydraulic material composition of the present invention includes an AE agent, the mixing ratio of the shrinkage reducing agent for the hydraulic material and the AE agent in the hydraulic material composition (mass of the shrinkage reducing agent) / (mass of the AE agent). Is preferably 99.98 / 0.02 to 80/20. With such a blending ratio, the hydraulic material composition is excellent in both shrinkage reduction performance and freeze-thaw resistance. The blending ratio is more preferably 99.96 / 0.04 to 85/15, still more preferably 99.9 / 0.1 to 90/10, and particularly preferably 99.8 / 0. 2 to 90/10.
Such a hydraulic material composition comprising the shrinkage reducing agent for hydraulic material, the hydraulic material and the AE agent of the present invention, wherein the content of the AE agent is 0.002 with respect to 100 parts by weight of the hydraulic material. A hydraulic material composition that is not less than part by weight and has a mass ratio of the shrinkage reducing agent for hydraulic material to the AE agent of 99.98 / 0.02 to 80/20 is also one aspect of the present invention.

The AE agent contained in the hydraulic material composition of the present invention is not particularly limited as long as it functions as an AE agent. For example, resin soap, saturated or unsaturated fatty acid or salt thereof, sodium hydroxystearate, lauryl sulfate ABS (alkyl benzene sulfonate), LAS (linear alkyl benzene sulfonate), alkyl naphthalene sulfonic acid or its salt, alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or Salts thereof, polyoxyethylene alkyl (phenyl) ether phosphates or salts thereof, protein materials, alkenyl sulfosuccinic acid, α-olefin sulfonate, polyoxyethylene sorbitan oleate, etc. That.
Among these, resin soap, saturated or unsaturated fatty acid or salt thereof, ABS (alkyl benzene sulfonate), LAS (linear alkyl benzene sulfonate), polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) Ether sulfate or its salt, polyoxyethylene sorbitan oleate are preferable, resin soap, ABS (alkyl benzene sulfonate), LAS (linear alkyl benzene sulfonate), polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (Phenyl) ether sulfate or a salt thereof, polyoxyethylene sorbitan oleate is particularly preferred.

From the point of making the hydraulic material composition of the present invention excellent in freeze-thaw resistance, it is preferable that the foam present in the hydraulic material composition is fine, and with the addition of a shrinkage reducing agent, etc. It is preferable to include an antifoaming agent in order to eliminate large bubbles contained in the composition.
When the hydraulic material composition of the present invention contains an antifoaming agent, the blending ratio of the hydraulic material shrinkage reducing agent and the antifoaming agent (the mass of the shrinkage reducing agent) / (the mass of the antifoaming agent) is 99. It is preferably 99 / 0.01 to 85/15. With such a blending ratio, the hydraulic material composition is excellent in both shrinkage reduction performance and freeze-thaw resistance. The blending ratio is more preferably 99.98 / 0.02 to 90/10, still more preferably 99.96 / 0.04 to 90/10, and particularly preferably 99.95 / 0. 05-95 / 5.

As described above, in order to improve the freeze-thaw resistance of the hydraulic material composition, it is preferable to reduce large bubbles in the hydraulic material composition, and for this purpose, a shrinkage reducing agent for the hydraulic material. It is preferable to use a shrinkage reducing agent such that the cell spacing coefficient by an air void analyzer of a mortar composition to which 0.7 mass% is added is 350 μm or less. Furthermore, by using an antifoaming agent, it is possible to eliminate large foams contained in the composition with the addition of a shrinkage reducing agent, etc., so that the freeze-thaw resistance of the hydraulic material composition can be further improved. .
A composition for a hydraulic material containing a shrinkage reducing agent and an antifoaming agent at a predetermined ratio, that is, a composition for a hydraulic material containing a shrinkage reducing agent for a hydraulic material and an antifoaming agent. The blending ratio of the hydraulic material shrinkage reducing agent and the antifoaming agent in the hydraulic material composition (mass of hydraulic material shrinkage reducing agent) / (mass of antifoaming agent) is 99.99 / 0.00. 01-85 / 15, characterized in that the bubble spacing coefficient by an air void analyzer of a mortar composition in which 0.7% by mass of the shrinkage reducing agent for hydraulic material is added to the hydraulic material can be adjusted to 350 μm or less. The hydraulic material composition is also one aspect of the present invention.
It is preferable that the composition for hydraulic material of the present invention further contains an AE agent. When the hydraulic material composition contains an AE agent in addition to the antifoaming agent, the hydraulic material composition obtained by adding the hydraulic material composition to the hydraulic material is more excellent in freeze-thaw resistance. It will be. When the composition for hydraulic materials of the present invention contains an AE agent, the content of the AE agent is preferably the same as the content when the above-described hydraulic material composition contains an AE agent.
That is, the composition for hydraulic material of the present invention further contains an AE agent, and the mixing ratio of the shrinkage reducing agent for hydraulic material and the AE agent in the composition for hydraulic material (of the shrinkage reducing agent for hydraulic material). It is one of the suitable forms of the composition for hydraulic materials of this invention that (mass) / (mass of AE agent) is 99.98 / 0.02-80 / 20.

Although it does not restrict | limit especially as long as it functions as an antifoamer as an antifoamer which the hydraulic material composition of this invention contains, For example, 1 of the antifoamers illustrated to the following (1)-(10) Species or two or more can be used.
(1) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.
(2) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.
(3) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.
(4) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.
(5) 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 oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) such as polyoxypropylene phenyl ether and polyoxyethylene nonyl phenyl ether Oxyalkylene (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 acetylene alcohol such as butyn-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 alkyl such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate salts; (Poly) oxypolyethylene stearyl phosphate, etc. (poly) Xylene polyoxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide; and the like.
(6) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, 2-ethylhexyl alcohol, acetylene alcohol, glycols and the like.
(7) Amide antifoaming agent: acrylate polyamine and the like.
(8) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.
(9) Metal soap antifoaming agents: aluminum stearate, calcium oleate, etc.
(10) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil, and the like.

When the hydraulic material composition of the present invention contains other materials such as the above-mentioned water reducing agent, AE agent (air entraining agent), antifoaming agent, etc., the hydraulic material composition of the present invention reduces shrinkage for hydraulic materials. It can also be said that the composition for hydraulic materials containing an agent and a polycarboxylic acid-based water reducing agent and other materials is included. Such a composition for a hydraulic material containing a shrinkage reducing agent for a hydraulic material and a polycarboxylic acid-based water reducing agent and other materials is also one aspect of the present invention.
When the composition for hydraulic material of the present invention contains an AE agent or an antifoaming agent, the preferred blending ratio of the shrinkage reducing agent for hydraulic material and those agents is the same as the preferred blending ratio in the hydraulic material composition. It is.

The composition for hydraulic material of the present invention is characterized in that the bubble spacing coefficient by an air void analyzer of a mortar composition in which 0.7% by mass of a shrinkage reducing agent for hydraulic material is added to cement can be adjusted to 350 μm or less. It is preferable that it is a composition to be. In order to improve the freeze-thaw resistance of the hydraulic material composition, it is preferable to reduce large bubbles in the hydraulic material composition. The bubble spacing coefficient is an index of the size of air bubbles in the hydraulic material composition. If the bubble spacing coefficient measured in this way is 350 μm or less, it can be said that there are few large bubbles. The bubble spacing coefficient is more preferably 330 μm or less, still more preferably 300 μm or less, and particularly preferably 280 μm or less. The bubble spacing coefficient is usually 120 μm or more.

The admixture composition of the present invention has the above-described configuration and can sufficiently exhibit both shrinkage reduction and fluidity of the cement composition, and therefore can be suitably used for hydraulic material compositions and the like. .

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

The molecular weight of the polymer, polyalkylene glycol compound or unsubstituted polyamine compound was measured as follows.
<Molecular weight measurement (GPC analysis method)>
Device: Waters Alliance (2695)
Analysis software: Waters, Empor professional + GPC option column: Tosoh Co., Ltd., TSK guard columns α + TSK gel α5000 + α4000 + α3000
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution prepared by dissolving 30.4 g of boric acid 93.98 g and sodium hydroxide in a mixed solvent of 15076 g of water and 3800 g of acetonitrile. (50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of the polyethylene glycol.
Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection amount: 100 μL
Sample concentration: adjusted to 1% with eluent.

(Production Example 1) Production of polymer 1 90.3 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device. Displacement and heating to 92 ° C. under a nitrogen atmosphere. Methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide 23) 128.0 parts, 5.6 parts of methacrylic acid, 32.0 parts of water, 0.43 part of 30% aqueous sodium hydroxide and 3-mercapto as a chain transfer agent A monomer aqueous solution in which 0.71 part of propionic acid was mixed was dropped into the reaction vessel over 4 hours, and 42.0 parts of 1.5% ammonium persulfate was dropped into the reaction vessel over 5 hours. Further, the temperature was maintained at 92 ° C. for 1 hour to complete the polymerization reaction, and neutralized to pH 7.0 with a 30% aqueous sodium hydroxide solution to give an aqueous polymer solution having an acid amount of 36.1 mol% and a weight average molecular weight of 26000. (Polymer 1) was obtained. In addition, the said ratio of the amount of acid is a ratio of the monomer which has an acid group computed from the mole number of the monomer used for manufacture of a polymer.

(Production Example 2) Production of polymer 2 Methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide 23) 123.8 parts, 8.9 parts of methacrylic acid, 30.9 parts of water, 30% aqueous sodium hydroxide solution A polymer aqueous solution having an acid amount of 48.2 mol% and a weight average molecular weight of 24,000 was prepared in the same manner as in Production Example 1 except that 69 parts of monomer and 0.70 part of 3-mercaptopropionic acid were mixed as a chain transfer agent. (Polymer 2) was obtained.

Production Example 3 Production of Polymer 3 69.3 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device. Displacement and heating to 92 ° C. under a nitrogen atmosphere. 133.8 parts of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added 45), 4.6 parts of methacrylic acid, 57.4 parts of water, 0.35 part of 30% aqueous sodium hydroxide and 3-mercapto as a chain transfer agent A polymer aqueous solution (polymer 3) having an acid amount of 45.2 mol% and a weight average molecular weight of 11,000 was obtained in the same manner as in Production Example 1, except that an aqueous monomer solution mixed with 1.87 parts of propionic acid was used.

(Production Example 4) Production of Polymer 4 A thermometer, a stirrer, a dropping device, a nitrogen introducing tube and a reflux cooling device equipped with 91.3 parts of water were charged in a glass reaction vessel, and the inside of the reaction device was stirred with nitrogen. Substitution and heating to 80 ° C. under nitrogen atmosphere. Methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide 23) 123.3 parts, methacrylic acid 6.7 parts, hydroxyethyl acrylate 3.4 parts, water 30.8 parts, 30% aqueous sodium hydroxide 0.60 part In addition, an aqueous polymer solution having an acid amount of 36.1 mol% and a weight average molecular weight of 26500 (heavy weight) was prepared in the same manner as in Production Example 1, except that a monomer aqueous solution in which 0.91 part of 3-mercaptopropionic acid was mixed as a chain transfer agent. Combined 4) was obtained.

(Production Example 5) Production of polymer 5 A thermometer, a stirrer, a dropping device, a nitrogen introducing tube and a reflux cooling device equipped with 91.3 parts of water were charged in a glass reaction vessel, and the inside of the reaction device was stirred under nitrogen. Substitution and heating to 80 ° C. under nitrogen atmosphere. Methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide 23) 123.3 parts, 7.7 parts of methacrylic acid, 2.0 parts of hydroxypropyl acrylate, 30.8 parts of water, 0.60 part of 30% aqueous sodium hydroxide solution In addition, an aqueous polymer solution having an acid amount of 41.9 mol% and a weight average molecular weight of 21,000 (heavy weight) was prepared in the same manner as in Production Example 1, except that a monomer aqueous solution in which 0.91 part of 3-mercaptopropionic acid was mixed as a chain transfer agent. Combined 5) was obtained.

(Production Example 6) Production of polymer 6 A glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 200.0 parts of polyethylene glycol having a weight average molecular weight of 4500, and the nitrogen gas flow was 120. It melted by heating to ± 5 ° C. Next, while maintaining the temperature at 120 ± 5 ° C., 12.4 parts of acrylic acid and 2.5 parts of perbutyl D (trade name, manufactured by NOF Corporation, di-t-butyl peroxide) are separately added for 1 hour. Then, stirring was continued for 1 hour while maintaining the temperature at 120 ± 5 ° C., the heating was completed, and after cooling to 80 ° C., 200.0 parts of water was added, and further, a pH of 6. with 30% aqueous sodium hydroxide solution was added. 7 to obtain a polymer aqueous solution (polymer 6) having a weight average molecular weight of 5000 and an acid amount of 79.5 mol%.

(Production Example 7) Production of polymer 7 (1. Tosylation step)
In a glass reactor equipped with a stirrer, polyethylene glycol (PEG10000) having a weight average molecular weight of 10000 (10.86 parts), tosyl chloride (TsCl) (4.576 g), and triethylamine (Et ₃ N) (3.036 parts) , 200.0 parts of dichloromethane (CH ₂ Cl ₂ ) was charged. After reacting for 24 hours while stirring the reaction system, the salt was removed by filtration, and the filtrate was desolvated under reduced pressure to obtain a tosylated product of both ends of PEG10000 (PEG10000-2OTs).
(2. Thioacetylation process)
In a glass reactor equipped with a stirrer, 96.65 parts of PEG10000-2OTs, 2.467 parts of potassium thioacetate (CH ₃ COSK), and 100.0 parts of acetonitrile (CH ₃ CN) were charged. After reacting for 24 hours while stirring the reaction system, the salt was removed by filtration, and the solvent was removed under reduced pressure to obtain a PEG 10000 terminus thioacetylated product (PEG10000-2SAc).
(3. Hydrolysis step)
In a glass reactor equipped with a stirrer, 92.65 parts of synthesized PEG10000-2SAc and 100.00 parts of methanol (MeOH) were charged, PEG10000-2SAc was dissolved, and 1N sodium hydroxide (NaOH) aqueous solution was added. After 25.00 parts were added and stirred for 10 minutes, 25.00 parts of 1N hydrochloric acid (HCl) was added and stirred for another 10 minutes, dichloromethane was added to perform extraction, the organic layer was recovered, and the solvent was removed under reduced pressure. To obtain PAG dithiol compound 1.
(4. Block polymerization process)
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introducer, and a reflux cooling device was charged with 15.0 parts of ion-exchanged water, and the reactor was purged with nitrogen under stirring. Then, an aqueous solution (A) (acid aqueous solution) consisting of 2.680 parts of methacrylic acid (MAA) and 10.720 parts of ion-exchanged water (PW) was dropped into the solution over 4.0 hours, and (A) At the same time, the aqueous solution (B) consisting of 31.37 parts of PAG dithiol compound 1 and 62.74 parts of ion-exchanged water (PAG thiol aqueous solution) was added dropwise over 4.0 hours. In addition, at the same time as dropping of (A), the azo initiator 2,2′-azobis-2-methylpropionamidine hydrochloride [2,2′-azobis (2-methylpropionamidine) dihydrochloride] (manufactured by Wako Pure Chemical Industries, Ltd.) V-50) An aqueous solution (C) composed of 0.2830 parts and 8.843 parts of ion-exchanged water was added dropwise over 5.0 hours. Thereafter, after maintaining the temperature at 80 ° C. for 1 hour, the mixture was cooled to complete the polymerization, and neutralized to pH 6.5 with a 30% aqueous sodium hydroxide solution to have a weight average molecular weight of 11000 and a weight average molecular weight of 10,000. An aqueous copolymer solution (polymer 7) having an acid amount of 90.9 mol% having 5 mol of methacrylic acid chain at both ends with respect to 1 mol of polyethylene glycol was obtained.

(Production Example 8) Production of polymer 8 (1. Production of epoxidized poly (n = 100) ethylene glycol at both ends)
A glass reaction vessel equipped with a thermometer, a dropping device and a reflux condenser was charged with 10.00 parts of dehydrated tetrahydrofuran (THF), stirred with a magnetic stirrer, and further dissolved with 1.00 parts of sodium hydride while cooling with ice. I let you. After dissolution, while cooling with ice, a mixed solution of 50.00 parts of poly (n = 100) ethylene glycol and 40.00 parts of THF was slowly added dropwise over 0.5 hours, and the mixture was further stirred for about 5 minutes. Warmed to. 8.16 parts of epichlorohydrin was added dropwise over 0.5 hours while maintaining the internal temperature at 40 ° C., and the mixture was further stirred for 5 hours. Thereafter, a small amount of deionized water is added to treat the unreacted sodium hydride. Further, THF is distilled off by an evaporator, and the residue is dropped into 200 ml of diethyl ether, and the precipitate is collected and dried. Terminal epoxidized poly (n = 100) ethylene glycol was obtained.
(2. Production of polymer 8)
A glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser was charged with 48.5 parts of epoxidized poly (n = 100) ethylene glycol at both ends, heated to an internal temperature of 55 ° C., and stirred. A mixed solution of 2.87 parts of L-aspartic acid, 3.59 parts of 48% sodium hydroxide and 42.09 parts of water was slowly added dropwise over 1.0 hour while maintaining the internal temperature at 55 ° C. The mixture was further stirred for 2.5 hours to obtain a polymer aqueous solution (polymer 8) having a weight average molecular weight of 4800 and an acid amount of 66.7 mol%.

(Production Example 9) Production of polymer 9 In a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, Epomin SP-200 (polyethyleneimine having a number average molecular weight of 10,000; Nippon Shokubai Co., Ltd.) The product was charged with 123.7 parts, and the inside of the reaction vessel was purged with nitrogen under stirring, heated to 60 ° C. under a nitrogen atmosphere, and stirred. To this, 11.81 parts of methyl acrylate was added dropwise over 0.5 hour, and then the temperature was maintained at 60 ° C. for 1 hour to complete the addition reaction of methyl acrylate. Next, 18.80 parts of NaOH aqueous solution adjusted to 30 wt% and 340.5 parts of pure water were added, and then the temperature was raised to 70 ° C. to hydrolyze methyl acrylate over 1 hour. After completion of the hydrolysis, the temperature was lowered to 20 ° C. or less, and 37.9 parts of acetic acid was added, and the pH was adjusted to 8.4, whereby an aqueous polymer solution having a weight average molecular weight of 10450 and an acid amount of 91.7 mol% (polymer 9) was obtained.

Production Example 10 Production of Polymer 10 A glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser was added to Epomin SP-200 (polyethyleneimine having a number average molecular weight of 10,000; Nippon Shokubai Co., Ltd.) (Manufactured) A polymer aqueous solution (polymer 10) having a weight average molecular weight of 10300 and an acid amount of 87.9 mol% was obtained in the same manner as in Production Example 9, except that 102.5 parts and 6.43 parts of methyl acrylate were used. It was.

(Comparative Production Example 1) Production of Comparative Polymer 1 A comparative polymer aqueous solution (comparative polymer 1) having an acid amount of 61.3 mol% was obtained in the same manner as in Reference Example 4 of Japanese Patent No. 3179822.

(Comparative Production Example 2) Production of Comparative Polymer 2 A glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser was charged with 112.5 parts of polyethylene glycol having a weight average molecular weight of 6000 and acrylic acid of 28.7. A comparative polymer aqueous solution (comparative polymer 2) having an acid amount of 95.5 mol% was obtained in the same manner as in Production Example 6 except that the parts were used.

(Comparative Production Example 3) Production of Comparative Polymer 3 (1. Tosylation step)
In a glass reactor equipped with a stirrer, 33.33 parts of polyethylene glycol (PEG 1000) having an average addition mole number of ethylene oxide of 25, 13.75 parts of tosyl chloride (TsCl), and 9 of triethylamine (Et ₃ N) were added. PEG1000 tosylate (PEG1000-OTs) was obtained in the same manner as in the tosylation step of Production Example 7, except that .15 parts and 200.0 parts of dichloromethane were used.
(2. Thioacetylation process)
The same method as in the thioacetylation step of Production Example 7, except that 40.00 parts of PEG1000-OTs and 9.437 parts of potassium thioacetate (CH ₃ COSK) were used in a glass reactor equipped with a stirrer. To obtain a thioacetylated form of PEG1000 (PEG1000-SAc).
(3. Hydrolysis step)
A PAG was prepared in the same manner as in the hydrolysis step of Production Example 7, except that 43.572 parts of synthesized PEG1000-SAc and 70.00 parts of methanol (MeOH) were used in a glass reactor equipped with a stirrer. Dithiol compound 2 was obtained.
(4. Block polymerization process)
121.30 parts of methacrylic acid, 18.806 parts of 30% aqueous sodium hydroxide and 435.2 parts of ion-exchanged water in an aqueous acid solution, 37.50 parts of PAG dithiol compound 2 and 65.54 parts of ion-exchanged water in an aqueous PAG solution Acid amount 97 having 20 moles of methacrylic acid chain at both ends with respect to 1 mole of polyethylene glycol having a weight average molecular weight of 6430 and an average addition mole number of ethylene oxide of 25 by the same method as in the block polymerization step of Production Example 7 except that it is used A 6 mol% aqueous copolymer solution (Comparative Polymer 3) was obtained.

(Production Example 11) Production of polycarboxylic acid-based water reducing agent (PC-1) 1698 parts of water was charged into a glass reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube and reflux condenser, and stirred. The reaction vessel was purged with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 1668 parts of methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 25), 332 parts of methacrylic acid and 500 parts of water are mixed, and 16.7 parts of mercaptopropionic acid as a chain transfer agent are uniformly mixed. A monomer aqueous solution was prepared by mixing. This monomer aqueous solution and 184 parts of 10% ammonium persulfate aqueous solution were added dropwise over 4 hours, and after completion of the addition, 46 parts of 10% ammonium persulfate aqueous solution was further added dropwise over 1 hour. Subsequently, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and neutralized with a 30% aqueous sodium hydroxide solution to obtain a polymer aqueous solution (PC-1) having a weight average molecular weight of 23,800.

(Production Example 12) Production of polycarboxylic acid-based water reducing agent (PC-2) In a glass reaction vessel equipped with a thermometer, stirrer, dropping device, and reflux condenser, 72.26 parts of ion-exchanged water, 3-methyl- First, 127.74 parts of unsaturated alcohol in which 50 mol of ethylene oxide was added to 3-buten-1-ol was added, the temperature was raised to 65 ° C., and then 0.38 part of a 30% aqueous hydrogen peroxide solution was added thereto. 19.83 parts of a 40% aqueous acid solution was added dropwise over 3 hours, 0.35 part of 3-mercaptopropionic acid over 3 hours, and 6.99 parts of a 2.1% aqueous L-ascorbic acid solution over 3.5 hours. Subsequently, the temperature was maintained at 65 ° C. for 60 minutes to complete the polymerization reaction, the temperature was lowered to 50 ° C. or less, and neutralized so that the pH was changed from pH 4 to pH 7 with 79.12 parts of a 5.0% aqueous solution of sodium hydroxide. As a result, a polymer aqueous solution (PC-2) having a weight average molecular weight of 27,000 was obtained.

(Measurement of values of conditions (1) and (2) in the present invention)
A mortar conforming to JASS 5 M402 was prepared with the following formulation, and the above polymers 1 to 10, comparative polymers 1 to 3, and a weight average molecular weight of 1000, which are commercially available products, were measured by the following 15 strike flow and 0 strike flow measurement methods. Polyethylene glycol (PEG1000: comparative polymer 4), polyethylene glycol having a weight average molecular weight of 4500 (PEG4500: comparative polymer 5), and polyethyleneimine (PEI) having a number average molecular weight of 10,000 (SP-200: comparative polymer 6) In the present invention, condition (1): (15 shot flow value of the mortar composition containing the compound) / (15 shot flow value of the mortar not containing the compound) × 100, condition (2): (after 2 hours A ratio of 15 stroke flow values) / (ratio of 15 stroke flow values after 10 minutes) × 100 was measured. The results are shown in Table 1. (I) to (V) in Table 1 describe the classification of the polymer in the present invention described above, and each classification is as follows.
In addition, when adding a polymer (shrinkage reducing agent) to the mortar based on JASS5M402, it added so that the sum total of water and a polymer might be 225g.
(I): Polycarboxylic acid polymer (II): Graft polymer (III): (Poly) alkylene glycol block copolymer (IV): Chelate PEG polymer (V): Polyamine polymer

<Mortar according to JASS 5 M402>
Ordinary Portland cement (JIS R 5210 compliant) 450g
225 g of water (deionized water)
ISO sand (Cement Association) 1350g
Defoaming agent (addition of master air 404 (made by BASF Japan)) so that the amount of mortar air becomes ± 3% of shrinkage reducing agent added (plain)
<Kneading of mortar composition>
The mortar composition was kneaded according to the method of JIS R5201-1997 Annex 2 as follows. 225 g of each polymer or shrinkage reducing agent and antifoaming agent weighed and diluted with water to a solid content of 0.1% or 1.0% with respect to 100 parts by weight of cement was charged in a kneading bowl. 450 g of ordinary Portland cement was put in, and immediately started at a low speed (rotation speed 140 ± 5 rpm, revolution speed 62 ± 10 rpm). 30 seconds after starting, 1350 g of standard sand for cement strength test (as defined in 5.1.3 of JIS R5201-1997 Annex 2) was added over 30 seconds. After the sand was added, the kneading was further continued for 30 seconds at a high speed (spinning speed 285 ± 10 rpm, revolution speed 125 ± 10 rpm), and the kneading was suspended for 90 seconds. The mortar attached to the kneading bowl was scraped off during the first 15 seconds of the rest, and the mortar attached to the bottom was collected in the center. After the suspension, the kneading was again carried out at a high speed for 60 seconds to complete the kneading.
After completion of the kneading, the mortar was taken out from the kneading pot, and the amount of air was measured according to the method of JIS A1174-1978.
Furthermore, 10 minutes after kneading, the mortar was taken out from the kneading bowl, and the mortar flow was measured according to the method of JIS R5201-1997 shown below. The mortar after measurement of the air amount and the mortar flow value was put into a polybeaker having a capacity of 1000 ml, and the upper part of the container was covered and stored with a wet rag to prevent drying. Moreover, the whole mortar was stirred about 10 times using the stainless steel basket every hour after the kneading | mixing start.
Two hours after kneading, the entire mortar was stirred about 10 times using a stainless steel punch, and then the flow of 15 strokes was measured.

<Measurement of 0 strike flow and 15 strike flow of mortar composition>
The 0-stroke flow and 15-stroke flow measurement of the mortar composition were performed as follows according to the method of JIS R5201-1997.
Twice the mortar into a flow cone (upper inner diameter 70 ± 0.5 mm, lower inner diameter 100 ± 0.5 mm, height 60 ± 0.5 mm) placed in the center on a flow table wiped well with a dry cloth Put it in. Put it up to 1/2 height, hit the entire surface 15 times with a stick (diameter 20 ± 1 mm, length 200 mm), then put the mortar up to the top of the flow cone, hit the entire surface 15 times with the stick, If necessary, smooth the surface. Then, the diameter of the mortar which removed the flow cone right above and measured it was set as 0 flow value. After the 0-stroke flow measurement, the flow table was subjected to 15 falling motions in 15 seconds, and then the diameter of the spread mortar was measured to obtain a 15-stroke flow value.
The measurement of the diameter was performed in a direction recognized as the maximum diameter after spreading of the mortar and a direction perpendicular thereto, and the average value was set to 0 stroke and 15 stroke flow values.

<Examples 1 to 12 and Comparative Examples 1 to 15: Mortar fluidity and shrinkage reduction performance evaluation>
By the following methods, the polymers 1 to 10 or the comparative polymers 1 to 6 and the polycarboxylic acid-based water reducing agents PC-1 and PC-2 were combined to evaluate mortar fluidity and shrinkage reduction performance. The addition amount of each compound was adjusted so that the mortar fluidity was 180 to 200 mm.
Tables 2 and 3 show the addition amount of each compound, and the results of mortar fluidity and shrinkage reduction performance.

(Mortar kneading)
500g of normal Portland cement (JIS R 5210 compliant) with mortar shown below
225 g of water (deionized water) + additive
Oikawa land sand (removes sand with a particle size of 5 mm or more; density 2.69 g / cm ³ ) 1350 g
According to the method of JIS R5201-1997 Annex 2, it was performed in the same manner as the kneading of the mortar composition in the measurement of the values of the conditions (1) and (2) in the present invention described above. After kneading is finished, the mortar is taken out from the kneading bowl, and using a steel slump cone described in JIS A1171 (top inner diameter 50 ± 0.5 mm, lower end inner diameter 100 ± 0.5 mm, height 150 ± 0.5 mm), Specimens for measuring mortar fluidity and evaluating shrinkage reduction performance were prepared according to the following method.
<Measurement of mortar fluidity>
The slump cone is placed on a horizontally placed steel flat plate, and the mortar kneaded by the above method is packed to a height of about 1/2 of the slump cone, and pierced 15 times with a stick. After poking 15 times, stuff the mortar up to the top of the slump cone and poke 15 times with a stick. Furthermore, after the top surface of the mortar is leveled with the top surface of the slump cone, immediately the slump cone is gently pulled up vertically. Next, after confirming that the spread of the mortar stopped, the major axis of the spread mortar and the diameter perpendicular to the major axis were measured, and the average value was defined as the mortar fluidity.
<Shrinkage reduction performance evaluation>
(Creation of specimen)
The specimen (4 × 4 × 16 cm) used for the shrinkage reduction performance evaluation was carried out according to the method of JIS R 5201 Annex 2 using mortar kneaded according to the above-mentioned <Kneading of the mortar composition>.
Silicone grease was previously applied to the mold so that it could be easily removed, and gauge plugs were attached to both ends. Immediately after kneading, the mortar was put in a mold, sealed, stored at 20 ° C., and subjected to initial curing (sealing curing). One day later, the mold was removed, 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).
(Measurement of length change)
A dial gauge (manufactured by West Japan Testing Machine Co., Ltd.) was used according to JIS A1129-3 (dial gauge method). After wiping off the water on the surface of the specimen cured in still water for 6 days 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 in a constant temperature and humidity chamber set at a temperature of 20 ± 1 ° C. and a humidity of 60 ± 5%, and measured in a timely manner.
At this time, the shrinkage reduction rate represented by the following formula was calculated, and the value was such that the shrinkage could be reduced when the composition of the present invention was added with respect to the shrinkage amount of the reference mortar without using the composition of the present invention. It shows that shrinkage | contraction was able to be reduced, so that a value is large.

When the polymers 1 to 10 are used in Examples 1 to 12, compared with Comparative Examples 1 and 11 in which neither of these polymers is used in any combination of PC-1 and 2, it is equivalent with a smaller amount of water reducing agent added. The mortar fluidity of was shown. On the other hand, Comparative Examples 6 to 10 and 15 in which the polymers 1, 3, 4, 6, 8, and 9 were respectively used alone had a low mortar fluidity value, so that these polymers themselves were used. It was revealed that almost no effect of improving the mortar fluidity was observed. By combining a polymer that does not contribute to improvement of mortar fluidity alone with a polycarboxylic acid-based water reducing agent, the mortar fluidity can be improved even if the amount of the polycarboxylic acid-based water reducing agent is reduced. Is an effect that cannot be predicted by those skilled in the art.
In addition, by using the above polymers 1 to 10 as a shrinkage reducing agent, it is possible to show the same or better shrinkage reduction with a smaller addition amount than when PEG1000, PEG4500 and SP-200 are used as the shrinkage reducing agent. It became clear.

Claims (2)

An admixture composition comprising a shrinkage reducing agent for hydraulic material and a polycarboxylic acid-based water reducing agent,
The shrinkage reducing agent for hydraulic material contains at least one compound selected from the group consisting of the following (I) to (V):
(I):
Following formula (1);

(In Formula (1), R < ¹ > -R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R < ⁴ > O is the same or different and represents a C2-C18 oxyalkylene group. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, p represents a number of 0 to 5, q represents a number of 0 or 1. n represents an average addition mole of an oxyalkylene group. A structural unit (I) represented by the following formula (2):

(In the formula ^(2), R 6 ~R ⁸ are the same or different, a hydrogen atom, a methyl group or a _-. (Representing _CH 2) m COOZ 'group wherein, m is an integer from 0 to 2 , Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group, and Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). II)
In the polymer, the proportion of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of all the structural units, and the proportion of the structural unit (II) is 100% by mol with respect to all the structural units. 10 to 59 mol%, and the polymer (II) having a weight average molecular weight of 4000 to 32000:
Following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In Formula (3), V and W are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. OA ¹ and B ¹ O are the same or different and have 2 to 2 carbon atoms. 18 represents an oxyalkylene group, and f and g represent the average number of added moles of OA ¹ and B ¹ O, respectively, and f and g are the same or different and are 0 to 2000, and f + g = 1 to 2000. Y represents a residue of a compound having active hydrogen, and k and l are the same or different and are 0 to 6. However, k + 1 is 1 or more. A polymer obtained by graft polymerization of an ethylenically unsaturated monomer,
The ethylenically unsaturated monomer includes an unsaturated carboxylic acid monomer,
In the polymer, the proportion of the structural unit derived from the unsaturated carboxylic acid monomer is 0.1 to 12% by mass with respect to 100% by mass of all the structural units, and the weight average molecular weight of the polyether compound is The polymer (III) which is 1500 to 50000:
A copolymer having a structure in which a polymer chain derived from an ethylenically unsaturated monomer component (A) and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X),
The ethylenically unsaturated monomer includes an unsaturated anionic monomer,
In the copolymer, the proportion of the structural unit derived from the unsaturated anionic monomer is 1 to 30 mol with respect to 1 mol of the (poly) alkylene glycol chain to form a (poly) alkylene glycol chain (poly). ) (Poly) alkylene glycol block copolymer (IV) having an alkylene glycol weight average molecular weight of 1500 to 50000:
A polyalkylene glycol compound having an organic residue capable of adsorbing to at least one of a metal, a metal compound and a metal ion bonded to at least two ends of a linear or branched polyalkylene glycol chain,
In the polyalkylene glycol compound, the polyalkylene glycol forming the polyalkylene glycol chain has a weight average molecular weight of 1500 to 50000,
The organic residue is a polyalkylene glycol compound (V) having at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group:
A polyamine compound having an acid group-containing side chain,
The polyamine compound has a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid monomer, and the proportion of structural units derived from the unsaturated carboxylic acid monomer is the total structure. A polyamine compound having an acid group-containing side chain of 25 to 99 mol% with respect to 100 mol% of the unit A hydraulic material composition comprising a shrinkage reducing agent for hydraulic material, a polycarboxylic acid-based water reducing agent, and a hydraulic material,
The shrinkage reducing agent for hydraulic material contains at least one compound selected from the group consisting of the following (I) to (V).
(I):
Following formula (1);

(In Formula (1), R < ¹ > -R < ³ > is the same or different and represents a hydrogen atom or a methyl group. R < ⁴ > O is the same or different and represents a C2-C18 oxyalkylene group. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, p represents a number of 0 to 5, q represents a number of 0 or 1. n represents an average addition mole of an oxyalkylene group. A structural unit (I) represented by the following formula (2):

(In the formula ^(2), R 6 ~R ⁸ are the same or different, a hydrogen atom, a methyl group or a _-. (Representing _CH 2) m COOZ 'group wherein, m is an integer from 0 to 2 , Z ′ represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group, and Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). II)
In the polymer, the proportion of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of all the structural units, and the proportion of the structural unit (II) is 100% by mol with respect to all the structural units. 10 to 59 mol%, and the polymer (II) having a weight average molecular weight of 4000 to 32000:
Following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In Formula (3), V and W are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. OA ¹ and B ¹ O are the same or different and have 2 to 2 carbon atoms. 18 represents an oxyalkylene group, and f and g represent the average number of added moles of OA ¹ and B ¹ O, respectively, and f and g are the same or different and are 0 to 2000, and f + g = 1 to 2000. Y represents a residue of a compound having active hydrogen, and k and l are the same or different and are 0 to 6. However, k + 1 is 1 or more. A polymer obtained by graft polymerization of an ethylenically unsaturated monomer,
The ethylenically unsaturated monomer includes an unsaturated carboxylic acid monomer,
In the polymer, the proportion of the structural unit derived from the unsaturated carboxylic acid monomer is 0.1 to 12% by mass with respect to 100% by mass of all the structural units, and the weight average molecular weight of the polyether compound is The polymer (III) which is 1500 to 50000:
A copolymer having a structure in which a polymer chain derived from an ethylenically unsaturated monomer component (A) and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X),
The ethylenically unsaturated monomer includes an unsaturated anionic monomer,
In the copolymer, the proportion of the structural unit derived from the unsaturated anionic monomer is 1 to 30 mol with respect to 1 mol of the (poly) alkylene glycol chain to form a (poly) alkylene glycol chain (poly). ) (Poly) alkylene glycol block copolymer (IV) having an alkylene glycol weight average molecular weight of 1500 to 50000:
A polyalkylene glycol compound having an organic residue capable of adsorbing to at least one of a metal, a metal compound and a metal ion bonded to at least two ends of a linear or branched polyalkylene glycol chain,
In the polyalkylene glycol compound, the polyalkylene glycol forming the polyalkylene glycol chain has a weight average molecular weight of 1500 to 50000,
The organic residue is a polyalkylene glycol compound (V) having at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group:
A polyamine compound having an acid group-containing side chain,
The polyamine compound has a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid monomer, and the proportion of structural units derived from the unsaturated carboxylic acid monomer is the total structure. A polyamine compound having an acid group-containing side chain of 25 to 99 mol% with respect to 100 mol% of the unit