JP6832773B2 - Admixture material composition - Google Patents

Description

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

Since hydraulic materials provide a cured product with excellent strength and durability, they are widely used as cement compositions such as cement paste, mortar, and concrete, and are used to construct civil engineering and building structures. It has become an indispensable item.
As the hydraulic material, an admixture material which is a material other than cement, water, and aggregate is 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 the admixtures, and AE agents, water reducing agents, AE water reducing agents, high-performance water reducing agents, fluidizing agents, high. Performance Various additives such as AE water reducing agent and shrinkage reducing agent are used. Further, for the purpose of exhibiting more excellent performance, it is also considered to use a plurality of these additives in a mixed manner.
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-A-2002-293596 JP-A-2007-79671 Japanese Unexamined Patent Publication No. 2008-23086 Japanese Unexamined Patent Publication No. 2001-247346

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, shrinkage occurs. It was not sufficient in terms of both the reducibility and the fluidity of the cement composition, and there was room for improvement.

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

The present inventor has studied various shrinkage reducing agents that can be used in combination with a polycarboxylic acid-based water reducing agent, and found that when a compound having a specific structure is used in combination with a polycarboxylic acid-based water reducing agent, the amount of these additions is large. We have found that even a small amount is excellent in both shrinkage reduction property and fluidity of the cement composition, and have come up with the idea that the above problems can be solved brilliantly, and have arrived at 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 material composition containing a shrinkage reducing agent for hydraulic materials and a polycarboxylic acid-based water reducing agent, and the shrinkage reducing agent for hydraulic materials comprises the following (I) to (V). It is an admixture material composition containing at least one compound selected from the group.
(I):
The following formula (1);

(In the formula (1), R ^{1 to} R ³ represent the same or different hydrogen atom or methyl group. R ⁴ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. P represents a number from 0 to 5, q is a number of 0 or 1, and n is an average addition molar of an oxyalkylene group. The structural unit (I) represented by (a number of 7 to 300) representing a number and the following formula (2);

(In formula (2), R ^{6 to} R ⁸ represent the same or different hydrogen atom, methyl group or − (CH ₂ ) _m COOZ'group, where m is an integer of 0 to 2. , Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). A polymer having II) and
In the polymer, the ratio of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of the total structural unit, and the ratio of the structural unit (II) is 100 mol% with respect to the total structural unit. , 10-59 mol% and a weight average molecular weight of 4000-32000: Polymer (II):
The following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In the 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. Representing 18 oxyalkylene groups. 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, 0 to 2000, and f + g = 1 to 2000. Y represents the residue of the compound having active hydrogen. K and l are the same or different, 0 to 6. However, k + l is 1 or more.) A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer, the ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer, and the polymer is an unsaturated carboxylic acid-based simple substance. Polymer (III) in which the proportion of structural units derived from the weight is 0.1 to 12% by mass with respect to 100% by mass of all structural units, and the weight average molecular weight of the polyether compound is 1500 to 50,000. :
A copolymer having a structure in which a polymer chain (A) derived from an ethylenically unsaturated monomer component and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X). The ethylenically unsaturated monomer contains an unsaturated anionic monomer, and the copolymer has a structural unit derived from the unsaturated anionic monomer in an amount of 1 mol of a (poly) alkylene glycol chain. On the other hand, the weight average molecular weight of the (poly) alkylene glycol which is 1 to 30 mol and forms the (poly) alkylene glycol chain is 1500 to 50,000, and the (poly) alkylene glycol-based block copolymer (IV):
A polyalkylene glycol compound in which an organic residue exhibiting an adsorptive ability to 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. The polyalkylene glycol compound has a weight average molecular weight of 1500 to 50,000 of the polyalkylene glycol forming the polyalkylene glycol chain, and the organic residues are a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, and a sub. 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, wherein the polyamine compound has a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid-based monomer, and the unsaturated carboxylic acid-based compound. The present invention will be described in detail below as a polyamine compound having an acid group-containing side chain in which the proportion of structural units derived from the monomer is 25 to 99 mol% with respect to 100 mol% of all structural units.
It should be noted that a combination of two or more of the individual 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 materials contained in the admixture material composition of the present invention contains at least one compound selected from the group consisting of the above (I) to (V). In the present invention, by using a shrinkage reducing agent having such a specific structure in combination with a polycarboxylic acid-based water reducing agent described later, shrinkage is reduced as compared with a combination of an existing shrinkage reducing agent and a polycarboxylic acid-based water reducing agent. It has been found that the property is improved and the fluidity of the cement composition is improved.
In the following, details of each of the compounds (I) to (V) will be described.

<First form: compound of (I)>
The compound of the above (I) has the following formula (1);

(In the formula (1), R ^{1 to} R ³ represent the same or different hydrogen atom or methyl group. R ⁴ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. P represents a number from 0 to 5, q is a number of 0 or 1, and n is an average addition molar of an oxyalkylene group. The structural unit (I) represented by (a number of 7 to 300) representing a number and the following formula (2);

(In formula (2), R ^{6 to} R ⁸ represent the same or different hydrogen atom, methyl group _{or-(CH 2} ) _m COOZ'group, where m is an integer of 0 to 2. , Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). It is a polymer having II) and.
The polymer of the above (I) (hereinafter, also referred to as a polymer (I)) is a structural unit (I) represented by the above formula (1) and a structural unit (II) represented by the formula (2). Each may contain one type, or two or more types may be contained.

In the above formula (1), R ^{1 to} R ³ represent the same or different hydrogen atoms or methyl groups, 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 kinds of oxyalkylene groups are present, random addition is performed. Any addition form such as block addition or alternate addition may be used.
The - (R 4 ^O) - oxyalkylene group represented by is preferably an oxyalkylene group having 2 to 8 carbon atoms, 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. Ethylene oxide, propylene oxide and butylene oxide are more preferable, and ethylene oxide and propylene oxide are more preferable.

^{When the oxyalkylene group represented by − (R 4} O) − in the above formula (1) contains an oxyethylene group to which ethylene oxide is added, 50 to 100 oxyethylene groups are contained in 100 mol% of all oxyalkylene groups. It is preferably contained in mol%. By containing the oxyethylene group in such a ratio, it is possible to suppress the increase in air entrainment, facilitate the adjustment of the amount of air, and suppress the decrease in strength and freeze-thaw resistance. it can. It is more preferably 60 to 100 mol%, further preferably 70 to 100 mol%, particularly preferably 80 to 100 mol%, and most preferably 90 to 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, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, still more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Most preferably, it is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
The hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group and heptyl group. , 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 groups such as icosyl groups; cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl group, benzyl group, phenethyl group, o-, m- or p -Trill group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, aryl group such as pyrenyl group and the like can be mentioned. Of these, linear, branched or cyclic alkyl groups are preferred.

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

N in the above formula (1) represents the average number of moles of the oxyalkylene group added, and is a number of 7 to 300. If the average number of moles added exceeds 300, the air entrainment property becomes high and it becomes difficult to adjust the amount of air, which may cause a decrease in strength and a decrease in freeze-thaw resistance. The average number of moles of the oxyalkylene group added is preferably 7 to 150. It is more preferably 7 to 100, still more preferably 7 to 80, particularly preferably 7 to 50, and most preferably 7 to 30.

The monomer forming the structural unit (I) represented by the above formula (1) can be obtained by adding an unsaturated alcohol and / or an unsaturated carboxylic acid to an unsaturated carboxylic acid in an amount of a predetermined number of repetitions. Can be done. Further, a transesterification reaction between an alcohol and an unsaturated carboxylic acid obtained by adding an amount of alkylene oxide having a predetermined number of repetitions to an alcohol or phenol having a hydrocarbon group having 1 to 30 carbon atoms, and / or It can also be obtained by transesterification with an unsaturated carboxylic acid ester.

Examples of the unsaturated alcohol include vinyl alcohol, allyl alcohol, metallic alcohol, 3-butene-1-ol, 3-methyl-3-butene-1-ol, 3-methyl-2-butene-1-ol, and 2 −Methyl-3-butene-2-ol, 2-methyl-2-butene-1-ol, 2-methyl-3-butene-1-ol and the like are suitable.
Further, as the unsaturated carboxylic acid, acrylic acid, methacrylic acid and the like are suitable. Further, as the unsaturated carboxylic acid ester, alkyl esters of these unsaturated carboxylic acids and the like can be used.
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; and phenols such as phenol and paramethylphenol. Of these, alcohols having 1 to 3 carbon atoms such as methanol, ethanol and butanol are preferable.
As the alkylene oxide, the above-mentioned ones can be used.

^{R 6 to} R ⁸ in the above formula (2) represent the same or different hydrogen atom, methyl group or − (CH ₂ ) _m COOZ'group.
-(CH ₂ ) _{m In the} COOZ'group, Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Here, examples of the monovalent metal include lithium, sodium, potassium and the like. Examples of the divalent metal include magnesium, calcium, strontium, barium and the like. It should be noted that Z'is a divalent metal because any two or more of ^{R 6 to} R ⁸ _{are − (CH 2} ) _m COOZ'groups, and two of them, −COO−, are anhydrides. In the form of, or in the form of an anhydride with any one of ^{R 6 to} R ⁸ _{− (CH 2} ) _{m COOZ'group and COOZ.}

When the above Z'is an organic amine group, the organic amine group includes primary organic amine groups such as methylamine, ethylamine, propylamine, n-butylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine and phenylamine. Amine-derived groups; 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 groups derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine. Be done. Among these, alkanolamine groups such as ethanolamine group, diethanolamine group and triethanolamine group, and triethylamine group are preferable.
When Z'is a hydrocarbon group, the hydrocarbon group preferably has 1 to 30 carbon atoms. It is more preferably one having 1 to 20 carbon atoms, and even more preferably one having 1 to 12 carbon atoms. The hydrocarbon groups 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, phenanthryl, Examples thereof include aryl groups such as biphenylyl, benzhydryl, trityl and pyrenyl.

Of 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.
Further, 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) represent the same or different hydrogen atom, methyl group _{or-(CH 2} ) _m COOZ'group, among which _{the- (CH 2} ) _m COOZ' group. When, it is preferable that R ⁷ is a − (CH ₂ ) _m COOZ'group, and R ⁶ and R ⁸ are hydrogen atoms or methyl groups. It is also a preferable 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-based monomer, and the unsaturated carboxylic acid-based monomer is an unsaturated monocarboxylic acid-based monomer. Monomers, unsaturated dicarboxylic acid-based monomers, and the like are suitable. The unsaturated monocarboxylic acid-based monomer may be a monomer having one unsaturated group and one group capable of forming a carboanion in the molecule. For example, (meth) acrylic acid and 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 preferable.
The unsaturated dicarboxylic acid-based monomer may be a monomer having one unsaturated group and two groups capable of forming a carboanion in the molecule, and may be maleic acid, citraconic acid, mesaconic acid, etc. Citraconic acid, fumaric acid and the like, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like, anhydrides thereof, or half esters thereof are preferable.

The compound of the first form contains the structural unit (I) represented by the above formula (1) and the structural unit (III) other than the structural unit (II) represented by the above formula (2). You may have.
Examples of the monomer forming the other structural unit (III) include bifunctional (meth) acrylates such as hexanediol di (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,4. -Butandiol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate and other alkanediol mono (meth) acrylates, etc. 2-6 carbon atoms Hydroxyl-containing (meth) acrylate compounds having a hydroxyalkyl group; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl ethyl (meth) acrylate, methoxypropyl (meth) acrylate and other alkoxy group-containing (meth) acrylate compounds ) Acrylate compounds; amides of unsaturated monocarboxylic acid-based monomers and amines having 1 to 30 carbon atoms as described above, (meth) acrylamide, methyl (meth) acrylamide, (meth) acrylic alkylamide, Unsaturated amides such as N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms, or 2 to 500 moles of these glycols added. Diesters with (poly) alkylene glycol; half-amides with maleamic acid and glycols with 2 to 18 carbon atoms or (poly) alkylene glycols with 2 to 500 additional moles of these glycols; hexanediol di (meth) Polyfunctional (meth) acrylates such as acrylates, trimethylolpropan tri (meth) acrylates, trimethylol propandi (meth) acrylates; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (Meta) Acryloxypropyl Sulfonate, 3- (Meta) Acryloxy-2-Hydroxypropyl Sulfonate, 3- (Meta) Acryloxy-2-Hydroxypropyl Sulfonate, 3- (Meta) Acryloxy-2-hydroxypropyl Oxysulfobenzoate , 4- (Meta) acryloxybutyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropan sulfonic acid (meth) acrylamide, unsaturated sulfonic acids such as styrene sulfonic acid, and Those monovalent metal salts, divalent metals Salts, ammonium salts and organic amine salts; vinyl aromatics such as styrene, α-methylstyrene, bromostyrene, chlorostyrene, vinyltoluene, p-methylstyrene; α-olefins such as hexene, heptene, decene; methylvinyl 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 cyanes such as (meth) acrylonitrile, α-chloroacrylonitrile; vinyl acetate, propion Unsaturated esters such as vinyl oxy; 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; polydimethylsiloxane propylaminomaleamic acid, polydimethylsiloxane aminopropylene aminomaleamine acid, poly Dimethylsiloxane-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-propyl-3-methacrylate) and other siloxane derivatives.

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

In the polymer (I), the ratio of the structural unit (II) represented by the above formula (2) is 10 to 59 mol% with respect to 100 mol% of the total structural unit. When the ratio of the structural unit (II) is in the above range, the amount of acid in the polymer (I) is in a suitable range, and the shrinkage reduction performance is excellent. The ratio of the structural unit (II) is preferably 20 to 55 mol%, more preferably 25 to 50 mol%.

In the polymer (I), the ratio of the other structural unit (III) is preferably 0 to 20% by mass with respect to 100% by mass of the total structural unit. It is more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.
When the polymer (I) essentially has the structural unit (III), the mass ratio of the structural unit (III) is preferably 1% by mass or more.

The polymer (I) has a total ratio of the structural unit (II) represented by the formula (2) and the other structural unit (III) of 3 to 25 mass% with respect to 100 mass% of the total structural unit. It is preferably%. It is more preferably 5 to 20% by mass, further preferably 5 to 15% by mass, and particularly preferably 7 to 15% by 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 further 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 the monomer component which is the raw material of the polymer by using a polymerization initiator.
The polymerization method of the monomer component is not particularly limited, and any commonly used polymerization method may be used, but the polymerization is preferably carried out by a method such as polymerization in a solvent or bulk polymerization.
Polymerization in a solvent can be carried out in a batch system or a continuous system, and the solvent used in this case is water; lower alcohols such as methyl alcohol, ethyl alcohol and 2-propanol; benzene, toluene, xylene, cyclohexane, etc. Examples include aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; and ketone compounds such as acetone and methyl ethyl ketone. Considering the solubility of the raw material monomer and the obtained polymer and the convenience of using 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, Japanese Patent Publication No. 2007-528397 can be referred to.

The polymer thus obtained may be used as it is as a drying shrinkage reducing agent, or may be handled in the form of an aqueous solution containing no organic solvent. In such a case, the polymer is further monovalent. Neutralized with alkaline substances such as metal and divalent metal hydroxides, chlorides and carbon salts; ammonia; organic amines (preferably monovalent 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.
Further, in the polymer thus obtained, a compound having an amino group and an imino group as described in International Publication No. 2007/08657, and / or a compound having an amino group, an imino group and an amide group. May contain an alkylene oxide-modified water-soluble polymer having a structure in which alkylene oxide is further added to a polymer skeleton bonded by grafting and / or cross-linking.

<Second form: compound of (II)>
The second form of the compound contained in the shrinkage reducing agent for hydraulic materials is the following formula (3);
^{_{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In the 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. Represents 18 oxyalkylene groups. 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, 0 to 2000, and f + g = 1 to 2000. Y represents the residue of the compound having active hydrogen. K and l are the same or different, 0 to 6. However, k + l is 1 or more.) A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer, the ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer, and the above-mentioned polymer is an unsaturated carboxylic acid-based simple substance. A polymer in which the ratio of structural units derived from a weight is 0.1 to 12% by mass with respect to 100% by mass of all structural units, and the weight average molecular weight of the polyether compound is 1500 to 50,000.

The above-mentioned graft polymer (hereinafter, also referred to as polymer (II)) is obtained by graft-polymerizing 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 the present invention, the action of the polyether chain and the graft chain has an action of sufficiently suppressing the progress of drying shrinkage of the cured product (hereinafter, also referred to as shrinkage reduction performance). In the preparation of the hydrophilic graft polymer, one kind of ethylenically unsaturated monomer and one kind of polyether compound may be used, or two or more kinds may be used in combination.

The ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer. The unsaturated carboxylic acid-based monomer is a monomer having at least one polymerizable unsaturated bond and one carboxyl group in the molecule, and contains α, β-unsaturated dicarboxylic acid and / or its anhydride. It is preferable to include it. This makes it possible to prevent sudden thickening due to runaway of the polymerization reaction in the above-mentioned graft polymerization.

In the polymer (II), the ratio of structural units derived from unsaturated carboxylic acid-based monomers is 0.1 to 12% by mass with respect to 100% by mass of all structural units. The ratio of the structural unit derived from the unsaturated carboxylic acid-based 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 its anhydride, the same one as the unsaturated dicarboxylic acid-based monomer in the polymer (I) described above can be used.

The content of α, β-unsaturated dicarboxylic acid and / or its anhydride in the unsaturated carboxylic acid-based monomer is, for example, to prevent thickening by graft-polymerizing the polyether compound at an appropriate rate. Is preferably 0.1 to 99.9% by weight. It is more preferably 1 to 99% by weight, further preferably 10 to 90% by weight, and most preferably 20 to 80% by weight.

The unsaturated carboxylic acid-based monomer also preferably contains an unsaturated carboxylic acid-based monomer other than the α, β-unsaturated dicarboxylic acid. As the unsaturated carboxylic acid-based monomer, the same one as the unsaturated monocarboxylic acid-based monomer in the first embodiment described above can be used.

In the present invention, one of the preferred embodiments of the unsaturated carboxylic acid-based monomer requires at least one selected from the group consisting of maleic acid, fumaric acid and maleic anhydride, and (meth) acrylic acid. It is to be included as an ingredient. The weight ratio of (meth) acrylic acid in such an embodiment 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. Is preferable. It is more preferably 10/90 to 90/10, even more preferably 20/80 to 80/20, and most preferably 30/70 to 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 alkyl esters of maleic acid such as monomethyl maleate, dimethyl maleate, monoethyl maleate, and diethyl maleate; monomethyl fumarate, dimethyl fumarate, and 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 hydroxyl groups such as hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylates; (methoxy) polyethylene glycol (meth) acrylates, phenoxypolyethylene glycol (meth) acrylates, naphthoxypolyethylene glycols ( Examples thereof include polyalkylene glycol (meth) acrylates such as meta) acrylate, monophenoxy polyethylene glycol maleate, and carbazole polyethylene glycol (meth) acrylate.

Examples of the ethylenically unsaturated monomer other than the above ethylenically unsaturated carboxylic acid esters include those described below. Aromatic vinyl-based monomers such as styrene; Vinyl-based monomers having an amide group such as (meth) acrylamide and (meth) acrylic alkylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate , Vinyl esters such as vinyl silicate; Alkenes such as ethylene and propylene; Dienes such as butadiene and isoprene; Vinyl-based monomers having a trialkyloxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane. Vinyl-based monomers having a silicon atom such as γ- (methacryloyloxypropyl) trimethoxysilane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dotecylmaleimide, stearylmaleimide, phenylmaleimide , Cyclohexyl maleimide and other maleimide derivatives.

Vinyl-based monomers having a nitrile group such as (meth) acrylonitrile; Vinyl-based monomers having an aldehyde group such as (meth) achlorein; dialkylaminoethyl (meth) acrylate such as dimethylaminoethyl (meth) acrylate Vinyl-based monomers having an amino group such as; unsaturated ethers such as (methoxy) polyethylene glycol (meth) allyl ether, (methoxy) polyethylene glycol isopropenyl ether; 2-acrylamide-2-methylpropanesulfonic acid , (Meta) allyl sulfonic acid, 2-sulfoethyl (meth) acrylate, vinyl sulfonic acid, hydroxyallyloxypropane sulfonic acid, styrene sulfonic acid and other vinyl-based monomers having a sulfonic acid group; vinyl chloride, vinylidene chloride, Vinyl-based monomers having other functional groups such as allyl chloride, allyl alcohol, vinyl pyrrolidone, and ethyl vinyl ether.

The amount of the ethylenically unsaturated monomer other than the unsaturated carboxylic acid-based monomer used is preferably 0.1 to 20% by mass based on the total amount of the ethylenically unsaturated monomer. It is more preferably 0.1 to 10% by mass, and even more preferably 0.1 to 5% by 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 and the ethylenically unsaturated monomer. It is preferable that the unsaturated carboxylic acid-based monomer in the monomer is a graft polymer obtained by graft-polymerizing the unsaturated carboxylic acid-based monomer 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 not easily act on the water-hard material and the shrinkage reduction performance may not be sufficient. If it exceeds 50% by weight, the hydrophilic graft polymer causes water. There is a risk that the curing retardability of the hard material will increase, and that the viscosity of the reaction mixture when preparing the hydrophilic graft polymer will increase, making it difficult to handle. It is more preferably 0.5 to 30% by weight, still more preferably 1 to 20% by weight, and particularly preferably 2 to 10% by weight.

In the polymer (II), the monomer components that are the raw materials of the compound are the polyether compound that is the raw material of the graft polymer, the unsaturated carboxylic acid-based monomer, and the unsaturated carboxylic acid-based monomer. It is an ethylenically unsaturated monomer other than the above, and the molar ratio of the polyether compound, the unsaturated carboxylic acid-based monomer, and the ethylenically unsaturated monomer other than the unsaturated carboxylic acid-based monomer. Is preferably 75 to 3/25 to 97/0 to 72. More preferably, it is 75 to 5/25 to 95/0 to 70, still more preferably 65 to 5/35 to 95/0 to 60, and particularly preferably 50 to 5/50 to 95/0 to 0. It is 45, 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 a graft polymer, and constitutes a polyether chain of the graft polymer. The balance between the hydrophilicity and the hydrophobicity of such a polyether compound directly affects the balance between the hydrophilicity and the hydrophobicity of the hydrophilic graft polymer. If the hydrophilicity of the graft polymer is too large, the cement dispersibility is improved, and as a result, material separation may occur, and the alkali resistance of the cured product may decrease. If the hydrophobicity is too large, the amount of air in the hydraulic material may be excessively reduced and the fluidity or the like may be lowered. Therefore, in the graft polymer of the second form, it is important to appropriately balance the hydrophilicity and the hydrophobicity of the polyether compound. As an index showing the balance between hydrophilicity and hydrophobicity, for example, there is HLB. To quantify the HLB, for example, according to the Griffin formula described in "Surfactant-Physical Properties / Applications / Chemical Ecology-" (8th print, August 10, 1991, published by Kodansha) by Kitahara et al. Can be calculated. The HLB of the above-mentioned polyether compound is preferably, for example, 8 to 20. It is more preferably 10 to 20, and even more preferably 13 to 19.

In the polymer (II), the polyether compound is a compound represented by the formula (3). As the compound represented by the above formula (3), one kind may be used, or two or more kinds may be used in combination.

In the above formula (3), V and W represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 30 carbon atoms. V and W are preferably hydrogen atoms or hydrocarbon groups 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, and particularly preferably, a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. And most preferably a hydrogen atom.
The hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group and heptyl group. , 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 groups such as icosyl groups; cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl group, benzyl group, phenethyl group, o-, m- or p -Trill group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, aryl group such as pyrenyl group and the like can be mentioned. Of these, linear, branched or cyclic alkyl groups are preferred.

In the above formula (3), the average number of moles added means the average value of the number of moles of the repeating unit in one mole of the compound represented by the above 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) indicate the average number of moles added of ^{OA 1} and B ^{1 O.} The f + g is preferably 25 or more from the viewpoints of improving the graft ratio of the graft polymer, improving the cement dispersion performance, improving the hydrophilicity, and the like. More preferably, it is 40 or more, and even more preferably 50 or more. Further, it is preferably 1000 or less, and more preferably 500 or less.

In the above formula (3), OA ¹ and B ¹ O represent "same or different" oxyalkylene groups having 2 to 18 carbon atoms, and f or g of them are present in the polyalkylene glycol. It means that the oxyalkylene groups of OA ¹ or B ^{1 O may all be the same or different.
Among the groups 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 kind or two or more kinds. There may be. When there are two or more kinds, the repeating form of the oxyalkylene group may be any of random, block, alternating and 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 number of moles of oxyalkylene groups having 2 to 18 carbon atoms is added. The ratio of the number of moles is preferably 50% or more. It is more preferably 60% or more, further 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. The active hydrogen means hydrogen to which an alkylene oxide can be added, and the residue of the compound having active hydrogen means a group having a structure obtained by removing the active hydrogen from the 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. Glycols having 2 to 18 carbon atoms; polyhydric alcohols having 3 to 24 carbon atoms such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, polyglycerin; ammonia, methylamine, ethylamine , Procylamine, butylamine, 2-ethylbutylamine, octylamine, dimethylamine, dipropylamine, dibutylamine, diphenylamine, trimethylamine, triethylamine, diethylenetriamine, triethylenetetramine and other amines having 1 to 30 carbon atoms; .. Among these, the compounds having active hydrogen are preferably monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, and 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, glycerin and polyglycerin. , More preferably, methanol, ethanol, propanol, butanol, ethylene glycol, trimethylolpropane, pentaerythritol, sorbitol, and even 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. And the like can be preferably applied. 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 if necessary, copolymerizable propylene oxide or the like. Further, in addition to the alkylene oxide having 2 to 18 carbon atoms, other alkylene oxides such as styrene oxide may be additionally contained if necessary.

The polymerization method in the preparation of the compound represented by the above formula (3) is not particularly limited, and for example, it is preferable to use a 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 semi-metal 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 alkaline catalyst include potassium hydroxide, sodium hydroxide, sodium hydride and the like. Each of these may be used alone, or two or more thereof may be used in combination.

The graft polymer of the second form may contain a derivative of the compound represented by the above formula (3) together with the compound represented by the above formula (3) as the polyether compound, and the above formula (3) may be used. Instead of the compound represented, a derivative of the compound represented by the above formula (3) may be contained. 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). Examples thereof include a crosslinked compound obtained by reacting the compound with a crosslinker having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group and a halogen group in one molecule.

As the terminal group converter, for example, the hydroxyl groups at all or a part of the compound represented by the above formula (3) are (i) fatty acids having 2 to 22 carbon atoms, sulfamic acid, and succinic anhydride. , Esterified with a dicarboxylic acid such as maleic acid, maleic anhydride, adipic acid and / or an anhydride thereof; (ii) alkoxylated by a dehalogenated hydrogen reaction using an alkyl halide, that is, alkoxypolyoxy. Alkylene; (iii) Sulfated with a known sulfuric acid agent such as chlorsulfonic acid, anhydrous sulfuric acid, sulfamic acid, that is, polyoxyalkylene sulfuric acid (salt) and the like.

The weight average molecular weight (Mw) of the compound represented by the above formula (3) is 1500 to 50,000. It is preferably 1500 to 40,000, more preferably 2000 to 35000, still more preferably 3000 to 35000, and particularly preferably 4000 to 25000. The degree of dispersion is not particularly limited, and is preferably 1 to 100, for example. It is more preferably 1.1 to 10, and even more preferably 1.1 to 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.

The graft polymerization for preparing the polymer (II) is carried out 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. It is said.

In the above-mentioned graft polymerization, the polyether compound may have a large number of graft sites in the same molecule or may not be present at all. Further, 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, a disproportionation termination reaction, a recombination termination reaction, etc., and is bonded to a polyether compound to form a dimer or a trimeric of the polyether compound, etc. Can be done. Therefore, it is considered that the molecular weight distribution of the obtained hydrophilic graft polymer is widened and the dispersity (Mw / Mn) is increased.

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

The graft polymer obtained by the above-mentioned graft polymerization may be used as it is, or may be used by dissolving it in a solvent. Examples of the solvent include water and alcohol, but it is preferable to use water. Further, a part or all of an acid group such as a carboxyl group or a sulfonic acid group or an ester group thereof contained in the hydrophilic graft polymer may be converted by a compound having a basic group. Thereby, the hydrophilic graft polymer can also be used as a salt.

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

<Third form: compound of (III)>
In the third form of the compound contained in the shrinkage reducing agent for water-hard materials, the end of the polymer chain (A) derived from the ethylenically unsaturated monomer component and the end of the (poly) alkylene glycol chain (B) are bonded sites. A copolymer having a structure bonded via (X), the ethylenically unsaturated monomer contains an unsaturated anion-based monomer, and the copolymer is an unsaturated anion-based single amount. The ratio 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 50,000. It is a (poly) alkylene glycol-based block copolymer.

The (poly) alkylene glycol-based block copolymer of the third form is a polymer chain (A) derived from a vinyl-based monomer (ethylene unsaturated monomer) component containing an unsaturated anion-based monomer. It is characterized by having a structure in which the ends of the polymer chain (B) due to the (poly) alkylene glycol-based structural unit are bonded via a binding site (X), thereby exhibiting an excellent shrinkage reducing effect. can do.
The structure of the (poly) alkylene glycol-based block copolymer of the third embodiment is not particularly limited as long as it has such structural characteristics, but the structure of the copolymer as a whole is not particularly limited, but a linear polymer chain (B). ) Is a copolymer having a structure in which only one end is bonded to the end of a polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer via a bond site (X). It is preferable to have.
The end of the polymer chain (A) that binds to the polymer chain (B) via the binding site (X) may be the end of the main chain of the polymer chain (A), and the polymer chain (A) When the side chain is bonded to the atom at the end of the main chain, it may be bonded to the end of the side chain, but it is preferably the end of the main chain.

The (poly) alkylene glycol-based block copolymer is described by 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 is a (poly) alkylene group. It represents a polymer chain based on a glycol-based structural unit, B represents an oxyalkylene group having 2 to 18 carbon atoms, which is the same or different. X represents an organic residue. A represents an unsaturated anionic monomer. Represents a polymer chain derived from a vinyl-based monomer component containing, n1 represents the average number of moles of an oxyalkylene group added, and is a number of 1 to 1000). Is preferable.

_{In the above formula (4), X located next to one end of the polymer chain (B) n1} according to the above (poly) alkylene glycol-based structural unit is a binding site (X), and is an unsaturated anion via X. The polymer chain A derived from the vinyl monomer component containing the system monomer is bonded to the _{polymer chain (B) n1 by the (poly) alkylene glycol-based structural unit. Further, at the other end of the polymer chain (B) n1} made of a (poly) alkylene glycol-based structural unit, 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-based monomer component containing the unsaturated anion-based monomer, the polymer chain (B) based on the (poly) alkylene glycol-based structural unit, and the binding site (X) will be described. ..

[Polymer chain (A) derived from a vinyl monomer component containing an unsaturated anion monomer]
In the third embodiment, the polymer chain (A) derived from the vinyl-based monomer component containing the unsaturated anion-based monomer is polymerized by the vinyl-based monomer component containing the unsaturated anion-based monomer. It is a structural unit having a structure.
Further, if the structural unit having a structure in which the vinyl-based monomer component containing the unsaturated anionic monomer is polymerized is a structural unit having the same structure, a structural unit derived from another monomer can be used. It may be denatured.

Examples of the unsaturated anion-based monomer include an unsaturated carboxylic acid-based monomer (hereinafter, also simply referred to as “monomer (a)”) and an unsaturated sulfonic acid-based monomer (hereinafter, simply “single”). Quantum (b) ”) and unsaturated phosphoric acid-based monomer (hereinafter, also simply referred to as“ monomer (c) ”) are preferable.
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 and a carbon number of 1. An alkyl group of 10 to 10 represents − (CH ₂ ) zCOOM ² (-(CH ₂ ) zCOOM ² may form an anhydride with COOM ¹ or other − (CH ₂ ) zCOOM ^{2), z.} Represents an integer from 0 to 2. M ¹ and M ² are the same or different, and have 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 (represented) is preferable.
That is, the monomer (a) is an unsaturated carboxylic acid-based 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 the polymerizable double bond of the monomer (a) represented by the above formula (5) is opened by the polymerization reaction (double bond (C =). C) corresponds to a structure) in which a single bond (-CC-) is formed.

In the above formula (5), the ^{groups represented by M 1} and M ² are monovalent metal atoms and divalent metal atoms, and the organic amine group is the monovalent metal atom in Z'of the above formula (2). , Divalent metal atom, organic amine group is the same as the specific example. Examples of the trivalent metal atom include aluminum and iron.
Specific examples of the unsaturated carboxylic acid-based monomer represented by the above formula (5) are the same as those of the monomer forming the structural unit (II) represented by the above formula (2). Among them, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and salts thereof are preferable from the viewpoint of polymerizable property, and acrylic acid, methacrylic acid and salts thereof are particularly preferable.

Examples of the monomer (b) include styrene sulfonic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt, amine salt or substituted amine salt thereof; sulfonethyl methacrylate, sulfopropyl methacrylate, sulfobutyl methacrylate. , Sulfonyl acrylates, sulfopropyl acrylates, sulfoalkyl (meth) acrylates such as sulfobutyl acrylates, 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, substituted amine salts and the like thereof are used. Preferably, it is styrene sulfonic acid or sulfoalkyl (meth) acrylate, or a salt thereof. Further, as the salt, an alkali metal salt is preferable.

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

The vinyl-based monomer component containing the unsaturated anion-based monomer may contain a vinyl-based monomer other than the unsaturated anion-based monomer.
As the vinyl-based monomer other than the unsaturated anion-based monomer, in addition to the compounds listed as specific examples of the monomer forming the other structural unit (III) in the compound of the first embodiment, Esters of unsaturated monocarboxylic acids such as methyl (meth) acrylate and glycidyl (meth) acrylate with 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 acrylates; Diesters of unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, and itaconic acid and alcohols having 1 to 30 carbon atoms; Diamides of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; alkyl (poly) alkylene glycols obtained by adding 1 to 500 mol of alkylene oxides having 2 to 18 carbon atoms to the alcohols and amines and the above non-polyethylene glycols. Diesters with saturated dicarboxylic acids; (poly) alkylene glycol di (meth) acrylates such as (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate; (polyethylene glycol dimalate and the like () Poly) alkylene glycol dimalates; vinyl ethers such as (methoxy) polyethylene glycol monovinyl ether, (methoxy) polyethylene glycol mono (meth) allyl ether or (meth) allyl ethers; (methoxy) polyethylene glycol 3-methyl-3-bu Examples thereof include 3-methyl-3-butenyl ethers such as tenyl ether, and one or more of these may be contained.

The vinyl-based monomer component containing the unsaturated anion-based monomer preferably contains 1 to 100% by mass of the unsaturated anion-based monomer with respect to 100% by mass of the entire vinyl monomer component. More preferably, it is 10 to 100% by mass, further preferably 50 to 100% by mass, and most preferably 100% by mass, that is, the vinyl-based monomer component is composed only of the unsaturated anionic monomer. Is to become.

In the (poly) alkylene glycol-based block copolymer in the third embodiment, the ratio of structural units 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 introduced in the unit is 1 to 30.
By setting the average number of moles to be introduced to 1 or more, it is possible to sufficiently exert the performance based on the polymer chain (A) by the unsaturated anion-based monomer unit in the copolymer.
Further, when the average number of introduced moles exceeds 30, the dispersibility is exhibited, so that the shrinkage reducing agent necessary for obtaining sufficient shrinkage reducing property cannot be added.
The average number of moles introduced is preferably 1 to 20, more preferably 2 to 15, and even more preferably 2 to 10.

In the (poly) alkylene glycol-based block copolymer in the third embodiment, the unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A) and the polyalkylene glycol chain The mass ratio with (B) is preferably 0.3 to 70 / 99.7 to 30. When the mass ratio of the unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A) is less than 0.3% by weight, the (poly) alkylene glycol-based block copolymer May become difficult to act on the water-hard material and the shrinkage reduction performance may not be sufficient. If it exceeds 70% by weight, the (poly) alkylene glycol-based block copolymer may increase the curing delay of the water-hard 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-based block copolymer in the third embodiment, the monomer components that are the raw materials of the compound are the monomer component that forms the polymer chain (A) and the polyalkylene glycol chain ( B) means. That is, the ethylenically unsaturated monomer component (vinyl-based monomer other than the unsaturated anion-based monomer and the unsaturated anion-based monomer) forming the polymer chain (A), and the polyalkylene glycol chain. (B), the number of moles of the unsaturated anionic monomer in the ethylenically unsaturated monomer component forming the polymer chain (A), and the number of moles of the polyalkylene glycol chain (B). The ratio of the number of moles to the vinyl-based monomer other than the unsaturated anionic monomer is preferably 25 to 97/75 to 3/0 to 72. More preferably, it is 50 to 97/50 to 3/0 to 47, still more preferably 65 to 95/35 to 5/0 to 30, and particularly preferably 80 to 95/20 to 5/0. It is 15.

[Polymer chain (B) with (poly) alkylene glycol-based structural unit]
The polymer chain (B) composed 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, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene. Examples thereof include monooxide and octylene oxide. Also, aliphatic epoxides such as dipentaneethylene oxide and dihexaneethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide. Epoxide or the like can also be used.

The alkylene oxide constituting the (poly) alkylene glycol-based 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 preferable. More preferably, it is mainly composed of alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and more preferably, it is mainly composed of ethylene oxide.

The term "main body" as used herein means that when the polymer chain (B) composed of the (poly) alkylene glycol-based structural unit is composed of two or more kinds of alkylene oxides, the (poly) alkylene glycol chain is composed of two or more kinds of alkylene oxides. It means that it accounts for the majority of the number of existence. When "occupying the majority" is expressed in mol% of ethylene oxide in 100 mol% of total alkylene oxide, 50 to 100 mol% is preferable. As a result, the (poly) alkylene glycol-based block copolymer in the present invention has higher hydrophilicity. It is more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

When the polymer chain (B) composed of the (poly) alkylene glycol-based structural unit is composed of two or more types of alkylene oxides, any of the forms such as random addition, block addition, alternate addition, etc. of two or more types of alkylene oxides. It may be added in.

The polymer chain (B) based on the (poly) alkylene glycol-based structural unit can be used as the (poly) alkylene glycol-based block copolymer in the third form when it contains an alkylene oxide having 3 or more carbon atoms. Since it is possible to impart a certain degree of hydrophobicity, when the above copolymer is used as a shrinkage reducing agent, it gives a slight structure (network) to the cement particles, and the viscosity and stiffness of the cement composition are felt. 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, and the antifoaming agent and the AE agent are mutually used. Since it becomes easy to act, it may cause a decrease in air content adjustability of concrete and mortar, and a resulting decrease in freeze-thaw resistance. Therefore, the content of the alkylene oxide having 3 or more carbon atoms with respect to 100% by mass of the total alkylene oxide is preferably 50% by mass or less. It is more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 10% by 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 end of the polymer chain (B) made of the (poly) alkylene glycol-based 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 alkylglycidyl ether residue. Of these, an oxypropylene group and an oxybutylene group are preferable because of ease of production.
When the oxyalkylene group having 3 or more carbon atoms is introduced, the amount to be introduced is preferably adjusted in consideration of the hydrolysis resistance of the binding site (X) in the block copolymer of the present invention, for example. , The introduction amount is preferably 50 mol% or more with respect to the polymer chain (B) composed of the (poly) alkylene glycol-based structural unit. It is more preferably 100 mol% or more, further preferably 150 mol% or more, and particularly preferably 200 mol% or more.

In the (poly) alkylene glycol-based block copolymer in the third embodiment, the average number of repetitions of alkylene oxide (average number of moles of oxyalkylene groups added) in the polymer chain (B) may be 1 to 1000. preferable.
When the average number of moles of the oxyalkylene group added is 1 or more, the copolymer can sufficiently exhibit the performance based on the polymer chain (B) by the (poly) alkylene glycol-based structural unit. ..
Further, when the average number of moles of the oxyalkylene group added exceeds 1000, the viscosity of the raw material compound used for producing the above-mentioned copolymer increases, the reactivity is not sufficient, and the workability is improved. It may not be suitable in terms of points.
The lower limit of the average number of added moles is more preferably 10, still more preferably 20, even more preferably 50, particularly preferably 75, particularly more preferably 80, and most preferably 100. Is. The upper limit is more preferably 800, even more preferably 700, even more preferably 600, particularly preferably 500, particularly more preferably 300, and most preferably 200.
The average number of repetitions of the alkylene oxide (average number of moles of oxyalkylene group added) means the average number of moles of alkylene oxide added in one branched portion.

Among the polymer chains (B) contained in the (poly) alkylene glycol-based block copolymer in the third form, the terminal of the polymer chain (B) that is not bonded to the polymer chain (A) via the binding site (X) is It is preferably either 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, 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 and naphthol. Either.
^{R 9} in the above formula (4) is preferably any of these.

The (poly) alkylene glycol compound forming the polymer chain (B) in the (poly) alkylene glycol-based 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 this is the case. The surface tension of the (poly) alkylene glycol compound is more preferably 55 to 65 mN / m, and even more preferably 57 to 65 mN / m.
<Surface tension measurement conditions>
Sample solution: 5% by mass aqueous solution of (poly) alkylene glycol compound Measuring device: Dynamic surface tension meter (SITAScience line t60 (manufactured by MESSTECHNIK))
<Measurement procedure>
(1) 200 parts by mass of ion-exchanged water at 25 ° C. is placed in a 300 ml glass beaker containing a 39 mm long stirrer chip, and the temperature is adjusted in an atmosphere of 25 ° C. while stirring with a magnetic stirrer. Add 100 parts by mass of ordinary Portland cement manufactured by Pacific Cement Co., Ltd. After charging, the rotation speed is set to 700 rpm, and the mixture is stirred for 30 minutes so that the water-soluble components in the cement particles are sufficiently eluted in water, and then allowed to stand for 10 minutes. This supernatant is suction-filtered using a filter paper (Advantech Toyo Co., Ltd., quantitative filter paper 5C), and then the filtrate is further filtered with an aqueous filter (chromatographic disk 25A, manufactured by Kurabou Co., Ltd., sold by GL Sciences) with a pore size of 0.45 μm. To obtain an aqueous solution of cement supernatant. The prepared cement supernatant is placed in a container, filled with nitrogen, and then sealed and stored.
(2) On the other hand, ion-exchanged water at 25 ° C. is added to (poly) alkylene glycol for measuring 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 sufficiently mixed to prepare a 5% by mass sample aqueous solution. The sample aqueous solution is placed in a container, filled with nitrogen, sealed, and the temperature is adjusted to 20 ° C.
(3) The surface tension of a 5% by mass solid content aqueous solution of (poly) alkylene glycol adjusted to 20 ° C. was measured using a dynamic surface tension meter (SITAScience line t60 (manufactured by MESSTECHNIK)). , Frequency 0.5 Hz is used as the surface tension of the corresponding compound.

[Binding site (X)]
In the (poly) alkylene glycol-based block copolymer in the third embodiment, the binding 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.
Preferred structures of the binding site include organic residues derived from the structure serving as a chain transfer agent used in the polymerization reaction.
Examples of the 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) and others. Structure-derived binding sites and the like can be mentioned.
The structures of organic residues existing at a plurality of binding sites may be the same or different.

(I) Bonding site containing a sulfur atom As the bonding site (X) containing a sulfur atom, a structure having an ester bond formed with the terminal oxygen atom of the polymer chain (B) and containing 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.
Examples of the binding site (X) containing the sulfur atom include 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, a phenyl group, an alkylphenyl group, a pyridinyl group, thiophene, pyrrole, furan, or thiazole and the like. (However, the structure represented by the aromatic group (however, it may be partially substituted with a hydroxyl group, an amino group, a cyano group, a carbonyl group, a carboxyl group, a halogen group, a sulfonyl group, a nitro group, a formyl group, etc.)) Can be mentioned.

^{R 14} of the structure represented by the above formula (6) is a site that binds to the polymer chain (B) due to the (poly) alkylene glycol-based structural unit, and the sulfur atom (S) contains an unsaturated anionic monomer. This is a site that binds to the polymer chain (A) derived from the vinyl-based monomer component.

The fact that the binding site (X) does not form an ester bond together with the terminal oxygen atom of the polymer chain (B) means that R ¹⁴ having the structure represented by the above formula (6) is a polymer composed of a (poly) alkylene glycol-based structural unit. When bonded to the terminal oxygen atom of the chain (B), the following formula (7):

(In the formula, R ¹⁴ is the same as above.) It will form the site indicated by, but does not contain an ester bond at this site.
Such a structure is obtained by tosylating the hydroxyl group at the terminal of the polymer chain (B) by the (poly) alkylene glycol-based structural unit, thioacetylating with thioacetic acid, and then hydrolyzing the terminal thiol as described later. It can be formed by block polymerization of an unsaturated carboxylic acid-based monomer (a) using a radical polymerization initiator using a group as a chain transfer agent.

On the other hand, the copolymer caused a dehydration esterification reaction between the carboxyl group of the mercaptocarboxylic acid and the hydroxyl group at the end of the polymer chain (B) due to the (poly) alkylene glycol-based structural unit, thereby obtaining the copolymer. When the unsaturated carboxylic acid-based monomer (a) is block-polymerized using a thiol ester as a chain transfer agent and a radical polymerization initiator, the binding site (X) is represented by the following formula (8):

(Wherein, R ¹⁵ is a mercapto carboxylic acid residue, for example, straight-chain or branched-chain alkylene group having 1 to 18 carbon atoms, a phenyl group, alkylphenyl group, pyridinyl group, thiophene, pyrrole, furan, thiazole, etc. The structure is represented by an aromatic group (however, it may be partially substituted with a hydroxyl group, an amino group, a cyano group, a carbonyl group, a carboxyl group, a halogen group, a sulfonyl group, a nitro group, a formyl group, etc.). ..
In this case, the binding site is the terminal oxygen atom of the polymer chain (B) formed by the (poly) alkylene glycol-based structural unit and the following formula (9):

(In the formula, R ¹⁵ is the same as above.) It will form the site indicated by, and will contain an ester bond at this site.

(Ii) Bonding Site Derived from Azo Initiator The binding site derived from the azo initiator is a site derived from a polymerization initiator containing an azo group (azo initiator), and is, for example, as shown in the following formula (10). Structures derived from the azo initiator are preferred.

(In the formula, R ¹⁶ is an alkylene group having 1 to 20 carbon atoms independently of each other (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 or the like). It may be a carbonyl group or a carboxyl group, or an alkylene group having 1 to 20 carbon atoms (the alkylene group may be an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, an amino group or the like. (Partially substituted) is a group bonded to a carbonyl group or a carboxyl group, and R ¹⁷ is an alkyl group having 1 to 20 carbon atoms and a carboxy substituent (with 1 to 10 carbon atoms) independently of each other. alkyl group, a phenyl group or substituted phenyl group, R ¹⁸ independently of one another, repeating units represented by the cyano group, an acetoxy group, a carbamoyl group or (alkoxy having 1 to 10 carbon atoms) carbonyl group.) An azo initiator having a
More preferably, an azo initiator represented by the following formula (11) can be mentioned.

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

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

This is the side where the carbon of the carbonyl group in the formula (13) is bonded to the polymer chain (B) of the (poly) alkylene glycol-based structural unit.

(Iii) Bonding site derived from a residue containing a phosphorus atom As a binding site containing a phosphorus atom, for example, the following formula (14):

(Wherein, Y1 is .M ³ represents 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) due to the (poly) alkylene glycol-based structural unit, and the phosphorus atom of the hypophosphorous acid (salt) that binds to Y1 is high due to the unsaturated anionic monomer unit. It is a 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, a divalent aromatic group having 6 to 30 carbon atoms (phenylene group, alkylphenylene group, and pyridine). Thiophen, pyrrole, furan, divalent group derived from thiazole, etc.), etc.), for example, hydroxyl group, amino group, acetylamino group, cyano group, carbonyl group, carboxyl group, halogen group, sulfonyl group, nitro group, formyl A group that may be partially substituted with a substituent such as a group is preferable.
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 organic residue having 2 to 8 carbon atoms. A alkylene group and a part thereof are substituted with a hydroxyl group.

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

(Iv) Binding Sites Derived from Other Structures Specific examples of 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-mentioned (i) binding site containing a sulfur atom.
For example, the -OH group at the end of the (poly) alkylene glycol is reacted with a thiocarboxylic acid such as thioacetic acid or thiobenzoic acid using zinc halide, and then alkaline hydrolysis is performed to obtain the -OH group. -Compound converted to SH group; (poly) By reacting diethyl (DEAD) azodicarboxylate with triphenylphosphine in the presence of alkylene glycol and thioacetic acid, and then performing alkaline hydrolysis, (poly) A compound in which the -OH group at the end of the alkylene glycol is converted to the -SH group; To a compound having a double bond such as an allyl group at the end of (poly) alkylene glycol, a thiocarboxylic acid such as thioacetic acid or thiobenzoic acid is added, and then alkaline hydrolysis is performed. -Compound 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 content of the sulfur atom in the entire (poly) alkylene glycol-based block copolymer in the present invention is preferably 0.001% by mass or more. .. More preferably, it is 0.005% by mass or more, and even more preferably, it is 0.01% by mass or more. The sulfur atom content is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less.
The sulfur atom content can be calculated from the average value of the sulfur atom content in the PAG thiol compound and the number of vinyl-based monomer units in the polymer chain (A) with respect to one thiol group (SH). When the content of the sulfur atom is within the above range, the (poly) alkylene glycol-based block copolymer in the third embodiment can be produced more efficiently by the production method described later.

As a preferable form of the (poly) alkylene glycol-based block copolymer in the third form, the polymer chain (A) and the polymer chain (A) after 15 minutes in a 2% by mass alkaline aqueous solution of the copolymer The decomposition rate into B) is 10% by mass or less. It is more preferably 5% by mass or less, and further preferably 2% by mass or less. Most preferably, it is substantially 0% by mass.
The decomposition rate referred to here is a hydrolysis rate in an alkaline aqueous solution, and when the hydrolysis rate is 10% by mass or less, it exhibits more excellent performance as a shrinkage reducing agent.
From the viewpoint of lowering the hydrolysis rate, the binding site (X) is preferably a non-ester bond having a sulfur atom.
As described above, it is one of the preferred embodiments of the present invention that at least one of the binding 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 according to the GPC measurement conditions described later, and is used 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 a 35% HCl aqueous solution to bring 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, and is used as the molecular weight after the reaction (after decomposition).
(3) The hydrolysis rate is calculated from the GPC chart before and after the reaction.

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

(In formulas (15) and (16), R ¹⁹ has the same or different 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. Represented. R ²⁰ represents the same or different hydrogen atom or methyl group. N5 represents the average number of moles of oxyethylene groups added, which 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 (poly) ethylene glycol chain, and the binding site (X) is thio. It is preferable that the structure is a binding site containing a sulfur atom derived from acetic acid or a metal salt thereof.

In the above formulas (15) and (16), ^{the positions of R 20} and the COOH group of the unsaturated carboxylic acid-based monomer unit are drawn on the hydrogen atom side at the end, but R ^{20 for each monomer unit.} And the position of the COOH group may be located on the sulfur atom side. In the structures represented by the above formulas (15) and (16), ^{whether the positions of the R 20} and the COOH group are on the hydrogen atom side or the sulfur atom side is randomly determined for each monomer unit.

[Method for producing (poly) alkylene glycol-based block copolymer]
As an example of the method for producing the (poly) alkylene glycol-based block copolymer of the third embodiment, the case of producing a copolymer having a bond site containing a sulfur atom derived from thioacetic acid (or a metal salt thereof) This will be described below.

The (poly) alkylene glycol-based block copolymer according to the third embodiment prepares a polymer chain (B) composed of a (poly) alkylene glycol-based structural unit having a hydroxyl group terminal at at least one terminal, and prepares the above-mentioned hydroxyl group. A step of carrying out a tosylation reaction with respect to a group terminal (tosylation step), a step of reacting with thioacetic acid or a metal salt thereof to carry out a thioacetylation reaction (thioacetylation step), and adding water to the thioacetyl group obtained by the thioacetylation step. Decomposition step (hydrolysis step), unsaturated vinyl monomer using a radical polymerization initiator using a polymer chain (B) consisting of a (poly) alkylene glycol-based structural unit having a thiol group at the end as a chain transfer agent. Can be produced by performing a step of block polymerization (block polymerization step).
A polymer chain (B) composed of a (poly) alkylene glycol-based structural unit having a thiol group at one end or both ends is also referred to as a PAG (di) thiol compound. When the (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 produced by reacting the hydroxyl group end of a polymer chain with a (poly) alkylene glycol-based structural unit having a hydroxyl group end at the end with a tosylating agent to generate tosylized (poly) alkylene glycol. Obtain a polymer chain according to the system constituent unit.
The tosylating agent and reaction conditions used in the tosylation step are not particularly limited as long as the hydroxyl group can be tosylated. For example, tosyl lolide (TsCl) is used as a tosylating agent and dichloromethane (CH ₂ Cl ₂ ) or the like is reacted. It may be used as a solvent and the reaction conditions may be set as appropriate.

[Thioacetylation step]
In the thioacetylation step, the tosyl group of the polymer chain obtained by the tosylation step and having a tosyl-terminated hydroxyl group terminal and having a tosyl group at the end (poly) alkylene glycol-based structural unit is reacted with the thioacetylating agent. To generate a thioacetyl group, a polymer chain consisting of a thioacetylated (poly) alkylene glycol-based structural unit is obtained.
The thioacetylating agent and the reaction conditions used in the above thioacetylation step 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. Is used as the reaction solvent, and the reaction conditions may be set as appropriate.

[Hydrolyzed step]
In the hydrolysis step, the thioacetyl group of the polymer chain obtained by the thioacetylation step, which is a (poly) alkylene glycol-based structural unit having a thioacetylated tosyl group terminal and a thioacetyl group at the terminal, is hydrolyzed to form a thiol group. To obtain a polymer chain with a (di) thiolated (poly) alkylene glycol-based structural unit. For example, PAG (di) thiol compounds represented by the following formulas (17) and (18) can be obtained.
The PAG (di) thiol compounds represented by the following formulas (17) and (18) are preferable as intermediates for producing the (poly) alkylene glycol-based block copolymer according to the present invention, respectively.
Also in the above hydrolysis step, the reaction conditions may be appropriately set so that the hydrolysis of the thioacetyl group proceeds.

(In formulas (17) and (18), R ⁹ , R ¹⁴ , and n1 are the same as 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, and by using this compound as a chain transfer agent and radically polymerizing a vinyl-based monomer component, the above The (poly) alkylene glycol-based block copolymer of the third form can be produced easily, efficiently, and at low cost.
Among the unsaturated anionic monomers contained in the vinyl-based monomer component, the unsaturated carboxylic acid-based monomer (monomer (a)) forming the polymer chain (A) is preferably the main component. It is preferable that substantially all of them are unsaturated carboxylic acid-based monomers forming the polymer chain (A).

The polymer obtained by the above polymerization reaction can be easily handled by adjusting the pH range to weakly acidic 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, if the polymerization reaction is carried out at a pH of 7 or higher, 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 carry out the polymerization reaction in an acidic to neutral pH range (preferably less than pH 6, more preferably less than pH 5.5, still more preferably less than pH 5).

[Method for producing a copolymer having a binding site other than the binding site containing a sulfur atom]
Up to this point, an example of producing a copolymer having a binding site containing a sulfur atom has been described, but a method for producing a copolymer having another structure as a binding site will be described below.

When producing a copolymer having a bond site derived from an azo initiator, a structure in which the end of the azo initiator is preliminarily bonded to the polymer chain (B) of the (poly) alkylene glycol-based structural unit by an ester bond as a starting material. Those having the above can be used.
An azo initiator having a structure in which the ends of the azo initiator are preliminarily bonded to the polymer chain (B) made of a (poly) alkylene glycol-based structural unit by an ester bond is, for example, an azo initiator having carboxyl groups at both ends of the azo group. It can also be obtained by esterifying (poly) alkylene glycol with Wako Pure Chemical Industries, Ltd., such as V-501. As a method for esterification, a manufacturing method that does not include a heating step is required because the azo initiator is decomposed when the heating step is performed. Such a production method includes (1) reacting an azo initiator with thionyl chloride to synthesize an acetate, and then reacting with (poly) alkylene glycol to obtain an azo initiator; (2) an azo initiator. And (poly) alkylene glycol are dehydrated and condensed with dicyclohexylcarbodiimide (DCC) and, if necessary, 4-dimethylaminopyridine to obtain an azo initiator; and the like.

When the above-mentioned azo initiator is used, the azo group is decomposed by heat to generate radicals, from which polymerization starts. Therefore, unsaturated anionic monomers are added one after another to one end of the polyalkylene oxide portion composed of the oxyalkylene group to form the (poly) alkylene glycol-based block copolymer of the third preferred form. To.

When producing a copolymer having a bond 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) due to the (poly) alkylene glycol-based structural unit. It is preferable to add hypophosphate (salt) to compound C having a group-bonded structure to produce a phosphorus atom-containing (poly) alkylene glycol-based compound.

The compound C can be synthesized by a known method.
The compound C may be synthesized by a method of adding a compound having an unsaturated group to the polymer chain (B) composed of a (poly) alkylene glycol-based 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 adding hypophosphorous acid (salt) to compound C, the ratio of hypophosphorous acid (salt) is 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, the amount of hypophosphorous acid (salt) is preferably 0.1 mol or more, more preferably 0.2 mol or more, still more preferably 0, based on 1 mol of the compound C. It is 5.5 mol or more. From the viewpoint of reducing unreacted hypophosphorous acid (salt), the amount of hypophosphorous acid (salt) is preferably 10 mol or less, more preferably 5 mol or less, still more preferably 1 mol of compound C. 2 mol or less.

The step of adding hypophosphorous acid (salt) to the compound C is preferably carried out at a temperature of 0 to 200 ° C. It is more preferably performed at a temperature of 20 to 150 ° C., further preferably 40 to 120 ° C., and even more preferably 50 to 100 ° C.

It is preferable to purify the obtained phosphorus atom-containing (poly) alkylene glycol-based compound after the step of adding a hypophosphorous acid (salt) to the compound C. The purification step can be carried out by drying the solution after the reaction to remove the solvent, suspending the solution in the purification solvent and performing filtration, and either or both of extraction.
The purification solvent may be appropriately selected, and for example, THF, acetonitrile, chloroform, isopropyl alcohol and the like are preferable.
The extraction solvent may be appropriately selected, but it is preferable to use 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 a low polar solvent.

The step of addition-reacting the compound C with the hypophosphorous acid (salt) can be carried out in a solution state dissolved in a solvent using a radical polymerization initiator, if necessary. Examples of the solvent used at that time 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; cyclic ether compounds such as tetrahydrofuran and dioxane. Above all, it is preferable to use water as a solvent.

When the step of addition-reacting the compound C with hypophosphorous acid (salt) is carried out 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 suitable because there is no radical. For example, persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; hydrogen peroxide; organic peroxides such as t-butylhydroperoxide; 2,2'-azobis-2-methylpropionamidine hydrochloride and the like. Azoamidin compounds, cyclic azoamidin compounds such as 2,2'-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, azonitrile compounds such as 2-carbamoyl azoisobutyronitrile, 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. Examples thereof include water-soluble azo-based initiators such as, and one or more of these can be used. Of these, a persulfate-based initiator is preferable.

The phosphorus atom-containing (poly) alkylene glycol-based compound has a function as a chain transfer agent, and by radically polymerizing an unsaturated anion-based monomer using this compound as a chain transfer agent, the above-mentioned first The (poly) alkylene glycol-based block copolymer of the preferred form of No. 3 can be produced easily, efficiently, and at low cost.
Since the step of radically polymerizing the unsaturated anionic monomer can be carried out in the same manner as the block polymerization step of using the PAG thiol compound as a chain transfer agent, detailed description thereof will be omitted.

<Fourth form: compound of (IV)>
The fourth form of the compound contained in the shrinkage reducing agent for water-hard materials is adsorbed on at least two ends of a linear or branched polyalkylene glycol chain with respect to at least one of a metal, a metal compound and a metal ion. A polyalkylene glycol compound to which an organic residue exhibiting a function is bonded, and the organic residue is selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphate group, a phosphite group and a silane group. It is a compound having at least one functional group and having a weight average molecular weight of 1500 to 50,000 for the polyalkylene glycol forming a polyalkylene glycol chain.

The compound in which an organic residue is bonded to at least two ends of the 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. Other structural sites may be included as long as they have at least three 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 parts are included, they may be the same or different.

The organic residue attached to the end of the polyalkylene glycol chain means an organic residue directly attached to the end of the polyalkylene glycol chain. Here, as the "terminal of the polyalkylene glycol chain", the end of the polyalkylene glycol chain whose end is unmodified (the end is a hydroxyl group) and the end of the polyalkylene glycol chain are modified as described later. Things and things are included. The structure in which an organic residue is bonded to the end of a polyalkylene glycol chain includes a hydroxyl group at the end of the polyalkylene glycol chain or a modified end by introducing a reactive functional group at the end of the polyalkylene glycol chain, and an organic described later. It can be formed by reacting with a compound that gives a residue. The reactive functional group is not particularly limited, and examples thereof include an amino group, a carboxyl group, and an epoxy group. It is preferably an epoxy group.

The fact that organic residues are bound to at least two ends of the polyalkylene glycol chain means that when the polyalkylene glycol chain is linear, organic residues are bound to both ends of the polyalkylene glycol chain. When the polyalkylene glycol chain has a branch, it means that an organic residue is bound to at least two ends of the main chain end and the branched chain end.

The organic residue is characterized by exhibiting an adsorptive capacity 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 on at least one of the metal, the metal compound and the metal ion contained in the cement composition.
The same applies to the form in which at least two terminal organic residues of the polyalkylene glycol chain are adsorbed on the same metal compound particles.
The cement particles contained in the above cement composition are tricalcium aluminate (C ₃ A: _{3 CaO · Al 2} O ₃ ) and tetracalcium iron aluminate (C ₄ AF: 4 CaO · 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 are adsorbed on such one cement particle, they are adsorbed on 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 phosphite group and a silane group, and is a vinyl-based single amount. It is a group that does not have a carbon-carbon bond derived from the body.
The functional group has an electron donating group having a lone electron pair, and forms a coordinate bond with at least one of a metal, a metal compound, and a metal ion to form a coordination bond with respect to 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 an adsorptive 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 coordinate-bonded to at least one of a metal, a metal compound and a metal ion by a plurality of coordination loci. That is, since the organic residue can be more strongly bonded to at least one of a metal, a metal compound and a metal ion by the chelating effect, it is more excellent in the cement additive's effect of suppressing deterioration of cement dispersion performance and drying shrinkage reduction performance. It becomes a thing.

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

The organic residue is a group having a molecular weight of 700 or less. When 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 suppression of deterioration of cement dispersion performance and reduction of drying shrinkage can be efficiently exhibited. The molecular weight of the organic residue is preferably in the range of 500 or less, more preferably 300 or less, 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 one 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 one of a carbonyl group, a hydroxyl group, an amino group or a phosphoric acid group.

The organic residue having a carbonyl group is not particularly limited as long as it has a carbonyl group, and also includes an organic residue having a functional group containing a carbonyl group such as a carboxyl group, an aldehyde group, an ester group and an amide group in the structure. .. 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 phosphite group and a silane group. Since such an organic residue can be more strongly bonded to at least one of a metal, a metal compound and a metal ion by the chelating effect, it is more excellent in the cement additive's effect of suppressing deterioration of cement dispersion performance and drying shrinkage reduction performance. It becomes a thing.

The organic residue is not limited as long as it exhibits an adsorptive ability to at least one of a metal, a metal compound and a metal ion, but the organic residue preferably has a catechol structure. It is also preferable that the organic residue 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 adsorptive ability for at least one of a metal, a metal compound and a metal ion.
The organic residue-containing polyalkylene glycol compound adsorbed on the metal or the like is filtered by dispersing the organic residue-containing polyalkylene glycol compound and the metal, the metal compound or the metal ion in the solution and then filtering the compound. Will be done. Therefore, by quantitatively analyzing the total amount of organic carbon in the filtrate and quantifying the organic residue-containing polyalkylene glycol compound that is not adsorbed with the metal contained in the filtrate, the total organic residue-containing polyalkylene is used. The ratio of the organic residue-containing polyalkylene glycol compound adsorbed to the metal or the like 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 described below at least two ends of the linear or branched polyalkylene glycol chain. It is obtained by binding compounds that give the organic residues described in detail.

The organic residue is a residue formed by binding a compound giving an organic residue to the end of a polyalkylene glycol chain, and the compound giving an organic residue is particularly limited to a vinyl-based monomer. Specific examples include, but are not limited to, the following compounds.
Amines such as ethylenediamine, diethylenetriamine, triaminotriethylamine, triethylenetetramine, N, N, N', N'-tetrakis (2-pyridylmethyl) ethylenediamine; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexacetic acid, tetra Ethylenepentamineheptaacetic acid, glycol etherdiaminetetraacetic 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' , 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-hexamethylene Diamine-N, N, N', N'-tetraacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodiacetic acid, 1,2-diaminopropane-N, N, N', N'-tetraacetic acid, tri Aminocarboxylic acids such as ethylenetetramine-N, N, N', N'', N''', N'''-hexacetic acid, glutamate, aspartic acid, aminosuccinic acid; hydroxyamines such as triethanolamine;

Tartrate, citric acid, 2,5-dihydroxy-tetracarboxylic acid-2,3,4,5-tetracarboxylic acid, 5-hydroxy-cyclohexane-1,2,3,4-tetracarboxylic acid, 6-hydroxy-tetracarboxylic acid-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 bicin; oxalic acid, maleic acid, succinic acid Polycarboxylic acids such as acids, 3-butene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; gluconic acid , Glucosamic acid, glucoheptonic acid lactone, gluconic acid lactone and other polyols; Tyrone, salicylic acid, sulfosalicylic acid, pyrogallolcarboxylic acid, Alizarin S, Alizarin complexone, Koji acid, 3- (3,4-dihydroxyphenyl)- Carboxylic acids such as L-alanine, 3-hydroxytyramine, DL-adrenaline; imidazoles such as histidine; pyrrolidones such as N-hydroxyethylpyrrolidone; ethylenediamine-N, N, N', N'-tetrakis (methylenephosphonic acid) ), Aminophosphates such as nitrilotris (methylenephosphonic acid); phosphates; phosphites; phosphonates; phosphinates; , Aminoethyl mercaptan, thiooxalic acid, thiosamines and other thiols; sulfurs such as sodium diethyldithiocarbamate, thiourea, thiocarbazide, thiosemicarbazide; monoalkoxysilane, dialkoxysilane, trialkoxysilane, acyloxysilane, triacyloxysilane, etc. Silanes; o-phenanthroline; acetylacetone; Eriochrome Black T, 1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3-naphthoic acid, hydroxynaphthol blue, chalcone, eriochrome. O, o'-dihydroxyazos such as Blue Black B, Eriochrome Blue SE, Eriochrome Red B, etc. 1-Pyridylazo-2-naphthol, 4- (2-pyridylazo) -resorcinol, 2- (2-pyridylazo) -p-cresol, 1- (2-thiazolylazo) -2-naphthol, 4- (2-thiazolylazo) -Resorcin, 2- (2-thiazolylazo) -p-cresol, trin, neotrin, 3- (4-sulfophenylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid sodium salt, naphthylazoxin, etc. Hydroxyazos;

Cresol phthalein complexon, thymolphthalein complexon, xylenol orange, methyltimol blue, pyrocatechol violet, pyrogallol red, brompyragrol red, chromazrol S, eryochrome cyanine R, glycintimol blue, glycine tremol red and other phthalein, sulfo Phthalene and triphenylmethanes; Murexide; Zincone; Thymol; Dithizone; Glyoxal bis (2-hydroxyanyl); N-benzoyl-N-phenylhydroxylamine; Galocyanin; Hematoxylin; Ferron; Calcein, Calcein blue, Fluoxin , Anicidin blue, thymolphthalein blue S, fluorin and other fluorescent metal indicators; variamine blue B base, bindshedras green leuco base, 3,3'-dimethylnaphthidine, cacoterin, diphenylcarbazide, diphenylcarbazone Redox indicators, etc.
In introducing the organic residue into the terminal of the polyalkylene glycol, one kind or two or more kinds of the above compounds can be used. Further, among the derivatives of these compounds, polyalkylene glycol, modified polyalkylene glycol described later, a compound having a functional group capable of reacting with polyalkylene glycol having an organic residue bonded to one end, and the like can also be used. ..

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

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

It is also useful to react the compound having a phosphonate group at the terminal of the polyalkylene glycol to introduce a phosphonate group. In this case, it is preferable to introduce a phosphonate group at the two terminals of the polyalkylene glycol, and such a compound is characterized by being represented by the following formula (19). This compound is obtained, for example, by the 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 represents the same or different alkylene group having 2 to 18 carbon atoms. R ²¹ , R ²² , R ²³ and R ²⁴ are independently -CH _2- PO (OM ⁴ _q2 ). Represents 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. M ⁴ is the same or different, hydrogen atom, alkali metal, alkaline earth metal, amine and / or organic amine residue. Representing a group. Q2 is 1 when M is any of a hydrogen atom, an alkali metal, an alkaline earth metal, an amine and / or an organic amine residue, and ^{1 / when M 4} is an alkaline earth metal. 2. n6 represents the average number of moles of oxyalkylene groups added, which is 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 formula (19) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

When a silane group is introduced by reacting the compound having a silane group at the terminal of the polyalkylene glycol, an alkoxysilane having 1 to 10 carbon atoms is preferable, and a trialkoxysilane is more preferable among the compounds having a silane group. Of these, compounds having -Si (OMe) ₃ and / or -Si (OCH ₂ CH ₃ ) ₃ are particularly preferable. Examples of the synthesis of such a compound include the reaction of 3- (trialkoxysilyl) propyl isocyanate with polyalkylene glycol or polyalkylene glycol diamine. In the reaction of the isocyanate group with the 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, at least two of these terminals may be denatured into organic residues by reacting the compound giving the organic residue with the organic residue to introduce the organic residue. The modification rate of the branched polyalkylene glycol chain of the present invention by an organic residue is preferably 20% or more, more preferably 40% or more, and further preferably 40% or more, based on the number of all terminals of the branched polyalkylene glycol chain of 100%. It is preferably 60% or more, particularly preferably 80% or more, and most preferably 100%. When the denaturation rate of the branched polyalkylene glycol chain of the present invention by the organic residue is 20% or more, the cement can be dispersed with a smaller amount of the cement additive, and the drying shrinkage reduction performance can be further exhibited. Can be done.

In the organic residue-containing polyalkylene glycol compound of the fourth form, the mass ratio of the polyalkylene glycol forming the polyalkylene glycol chain to the compound giving the organic residue used for forming the organic residue is poly. Polyalkylene glycols that form alkylene glycol chains / compounds that provide organic residues used to form organic residues = 99 to 1/1 to 99 are preferred. It is more preferably 98 to 10/2 to 90, further preferably 97 to 20/3 to 80, and particularly preferably 97 to 30/3 to 70.

In the organic residue-containing polyalkylene glycol compound of the fourth form, the monomer component which is the raw material of the compound is the polyalkylene glycol forming the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound and organic. 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 used to form an organic residue. The ratio of the compound to the number of moles is preferably 75 to 3/25 to 97. More preferably, it is 50 to 3/50 to 97, further preferably 40 to 3/60 to 97, particularly preferably 35 to 3/65 to 97, and most preferably 35 to 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. Further, it may have two or more kinds of polyalkylene oxides.
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. The carbon number of the oxyalkylene group is more preferably in the range of 2 to 8, and even more preferably in the range of 2 to 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. Be done. Also, aliphatic epoxides such as dipentaneethylene oxide and dihexaneethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide. Epoxide or the like can also be used.

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

The average number of moles of the oxyalkylene group added is preferably in the range of 1 to 1000. The lower limit of the average number of added moles is more preferably 25, further preferably 40, and particularly preferably 50. The upper limit is more preferably 800, still more preferably 700, particularly preferably 600, particularly preferably 500, even 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 50,000. It is preferably 1500 to 40,000, more preferably 2000 to 35000, still more preferably 3000 to 30000, and particularly preferably 4000 to 25000.
The dispersity of the polyalkylene glycol forming the polyalkylene glycol chain is not particularly limited, but is preferably 1 to 100, for example. It is more preferably 1.1 to 10, and even more preferably 1.1 to 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 embodiment, the weight average molecular weight of the polyalkylene glycol forming the polyalkylene glycol chain can be measured by GPC under the conditions described in Examples described later.

In the organic residue-containing polyalkylene glycol compound of the fourth form, 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 form. It is preferable that the surface tension measured under the above conditions is 55 to 70 mN / m. 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, branched polyalkylene glycol is synthesized by a method of sequentially adding an alkylene oxide 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 types of alkylene oxides, two or more types of alkylene oxides may be added in any form such as random addition, block addition, and alternate addition.

The metal to which at least two terminal organic residues of the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound are adsorbed is not particularly limited, and is, for example, a typical element and groups 8 and 9 of the periodic table. Examples include metals classified into Group 11 and Group 11 transition elements. Preferred examples include alkali metals, alkaline earth metals, and metal elements of groups 8, 10, 11, 12, 13 and 14 of the periodic table, and more preferably alkali metals and alkaline earths. It is a base metal such as metal, zinc, aluminum and iron.

The metal ion adsorbed by the organic residue is not particularly limited, and examples thereof include metal ions classified into main group elements and transition elements of groups 8, 9, 10 and 11 of the periodic table. Preferred examples include alkali metals, alkaline earth metals, and ions of metal elements of Group 8, Group 10, Group 11, Group 12, Group 13, and Group 14 of the periodic table, and more preferably alkali metals and alkalis. It is an ion of base metals such as earth metals, zinc, aluminum and iron.

<Fifth form: compound of (V)>
The fifth form of the compound contained in the shrinkage reducing agent for a water-hard material of the present invention is a polyamine compound having an acid group-containing side chain, and the polyamine compound is a structural unit derived from an unsubstituted polyamine compound and an unsaturated carboxylic acid. An acid group having a structural unit derived from an acid-based monomer and having a ratio of the structural unit derived from the unsaturated carboxylic acid-based monomer being 25 to 99 mol% with respect to 100 mol% of the total structural unit. It is a polyamine compound having an containing side chain.

The polyamine compound of the fifth form is an unsubstituted polyamine by reacting an unsaturated carboxylic acid-based monomer with the active amine hydrogen of the 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-based 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 polyamine compound of the fifth form, the ratio of structural units derived from unsaturated carboxylic acid-based monomers is 25 to 99 mol% with respect to 100 mol% of all structural units. It is preferably 30 to 97 mol%, more preferably 50 to 95 mol%.
In the following, 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 a secondary amino group in its molecule, and there are amines or derivatives thereof having such a group. Further, as the unsubstituted polyamine compound, one kind of compound may be used, or two or more kinds may be used. Further, the unsubstituted polyamine compound may have a structure of two or more of the following amines or derivatives thereof in the structure.
Examples of the amines include polyalkyleneimine obtained by polymerization or copolymerization of alkyleneimine (for example, ethyleneimine, azetidine, pyrrolidine, piperidine, etc.) such as polyethyleneimine obtained by polymerization of ethyleneimine; as described above. Polyalkyleneimine and / or polyamide obtained by condensing (poly) alkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine with polybasic acids such as sulfuric acid, phosphoric acid and adipic acid. Polyamines; polyalkyleneimines and / or polyureapolyamines obtained by reacting alkyleneimines with urea; polyamide polyesterpolyamines obtained by copolymerizing alkyleneimines with acid anhydrides such as phthalic anhydride; and allylamines, diallylamines and /. Or polyallylamine, diallylamine and / or polydialylamine-sulfur dioxide copolymer obtained by copolymerization of the hydrochloride and sulfur dioxide obtained by polymerization of the hydrochloride, diallylamine and / or its hydrochloride and maleic acid. Examples thereof include a diallylamine-maleic acid copolymer obtained by copolymerization.
Examples of the polyamine derivative 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 as the polyamine. Examples thereof include compounds that have undergone an 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 Catalyst Co., Ltd.), and polyallylamine PAA. -03, PAA-05, PAA-08, PAA-15, PAA-15B, PAA-10C, PAA-25 (Nitto Boseki Co., Ltd.), diallylamine / maleic acid copolymer PAS-410, PAS-410SA (Nitto Boseki Co., Ltd.) Commercial products such as (Co., Ltd.) can also be used.
Of these, polyalkyleneimine, polyamide polyamine, polyallylamine, polyethyleneimine, condensate of ethylenediamine and adipic acid, condensate of triethylenetetramine and adipic acid, and diallylamine-maleic acid copolymer are preferable, and polyalkyleneimine is preferable. , Polyamide polyamines and polyallylamines are particularly preferred.

The number average molecular weight of the unsubstituted polyamine compound is not particularly limited, but is preferably 1500 to 50,000. 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, so that sufficient drying shrinkage reduction property may not be obtained. On the contrary, 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 40,000, still more preferably 2000 to 35,000, 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 Examples.

The polyamine compound of the fifth form has a carboxyl group derived from an unsaturated carboxylic acid-based 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 It may have a side chain having a monovalent metal salt, a divalent metal salt, an ammonium salt, an organic amine salt and the like.
The side chain having a carboxyl group can be produced by reacting an unsaturated carboxylic acid-based monomer with a polyamine compound.
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 the carboxyl group, the atomic group that reacts with the amino group has a sulfonic acid group or a monovalent value thereof. 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, and 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 the amino group include an unsaturated hydrocarbon group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; a saturated hydrocarbon group having 1 to 20 carbon atoms, a glycidyl ether group, and an epoxy. Examples thereof include a group, an isocyanate group, a thioisocyanate group, an aldehyde group, a hydroxy group, and a group to which any one of a halogen atom is bonded.

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

In the polyamine compound having an acid group-containing side chain of the fifth embodiment, the monomer component which is 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-based 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-based monomer used as the monomer component is preferably 0.01 to 1 mol per active amine hydrogen of the unsubstituted polyamine compound. More preferably, it is 0.01 to 0.8 mol, further preferably 0.01 to 0.6 mol, particularly preferably 0.05 to 0.6 mol, and most preferably 0. .1 to 0.5 mol.

The amount of the acid group-containing compound used is preferably 0 to 0.5 mol per active amine hydrogen of the unsubstituted polyamine compound. More preferably, it is 0 to 0.3 mol, still more preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 0.3 mol, and most preferably 0.1. ~ 0.25 mol.

In the polyamine compound having an acid group-containing side chain of the fifth embodiment, the unsubstituted polyamine compound used for forming the polyamine compound having an acid group-containing side chain and the polyamine compound used for forming the acid group-containing side chain are used. The mass ratio with the acid group-containing compound is the unsubstituted polyamine compound used for forming the polyamine compound having the acid group-containing side chain / the acid group-containing compound used for forming the acid group-containing side chain = 99. It is preferably 9. to 50 / 0.1 to 50. When the mass ratio of the acid group-containing compound used for forming the acid group-containing side chain is less than 0.1% by weight, the polyamine compound having the acid group-containing side chain does not easily act on the water-hard material and shrinkage is reduced. The performance may not be sufficient, and if it exceeds 50% by weight, the polyamine compound having an acid group-containing side chain may increase the curing delay of the water-hard material. 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. It is 3 to 35.

In the polyamine compound having an acid group-containing side chain of the fifth embodiment, the number of moles of the unsubstituted polyamine compound used for forming the polyamine compound having an acid group-containing side chain and the acid group-containing side chain are formed. The ratio of the acid group-containing compound used for this purpose to the number of moles is preferably 75 to 3/25 to 97. It is more preferably 50 to 3/50 to 97, even more preferably 30 to 4/70 to 96, and particularly preferably 25 to 5/75 to 95.

The polyamine compound of the fifth form may have a side chain other than the acid group-containing side chain. Examples of other side chains include hydrocarbon group-containing side chains and oxyalkylene group-containing side chains.
The hydrocarbon group-containing side chain can be formed by reacting a polyamine compound with a compound having a structure in which a hydrocarbon group is bonded to an atomic group that reacts with an amino group.
The hydrocarbon group preferably has a hydrocarbon group having 1 to 30 carbon atoms, and may have a linear, branched, or cyclic structure. More preferably, it is 4 to 30 hydrocarbon groups. Further, as the hydrocarbon group, a linear, branched, cyclic alkyl group or aryl group is preferable.
As the atomic group (group) that reacts with the amino group, a carboxyl group, a group derived from carboxylic acid anhydride; a group derived from (meth) acrylic acid; a glycidyl ether group; an epoxy group; an isocyanate group; a thioisocyanate group; an aldehyde group; Hydroxyl group; halogen atom and the like can be mentioned.
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; octylcyclopentylglycidyl ether, octylcyclohexylglycidyl ether, nonylcyclopentylglycidyl ether, nonylcyclohexylglycidyl ether, laurylcyclopentylglycidyl Glycidyl ethers of alkylcycloalkanols such as ethers, laurylcyclohexylglycidyl ethers, stearylcyclopentylglycidyl ethers, stearylcyclohexylglycidyl ethers; alkylbenzyl alcohols such as octylbenzyl glycidyl ethers, nonylbenzylglycidyl ethers, laurylbenzyl glycidyl ethers and stearylbenzylglycidyl ethers. Glycidyl ethers; epoxy hexane, α-olefin epoxide which is a mixture of 12 to 14 carbon atoms, α-olefin epoxide which is a mixture of 16 to 18 carbon atoms, α-olefin epoxide which is a mixture of 20 to 28 carbon atoms, 1,2-Epoxyalkanes such as α-olefin epoxide which is a mixture of 30 or more carbon atoms; Alkyl isocyanates such as octyl isocyanate, decyl isocyanate and octadecyl isocyanate; Trirange with alcohols such as octanol, lauryl alcohol and stearyl alcohol. Monoisocyanate compounds obtained by reaction with diisocyanates such as isocyanate; halides in which the terminal hydroxyl groups of alcohols such as octanol, lauryl alcohol and stearyl alcohol are substituted with halogen atoms such as chlorine, bromine and iodine; lauric acid and myristine Saturated fatty acids such as acids, palmitic acid and stearic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and eleostearic acid; butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) 2-Ethylhexyl acrylate, (meth) lauryl acrylate, (meth) Examples thereof include (meth) acrylic acid esters such as myristyl acrylate and stearyl (meth) acrylate. One of these compounds may be used, or two or more of them may be used, but when two or more compounds are used, at least one of them is an epoxy group, an isocyanate group, a thioisocyanate group, or an aldehyde. A compound having a functional group selected from the group consisting of a group, an alkyl halide group, and an acyl halide group is preferable.

The amount of the compound having a structure in which a hydrocarbon group is bonded to the atomic group that reacts with the amino group is preferably 0.01 to 0.90 mol per active amine hydrogen of the unsubstituted polyamine compound. .. It is more preferably 0.05 to 0.90 mol, still more preferably 0.10 to 0.85 mol, particularly preferably 0.17 to 0.80 mol, and most preferably 0. It is .23 to 0.80 mol.

The oxyalkylene group-containing side chain can be obtained by adding a compound having an alkoxy group to one end of a (poly) alkylene oxide or a (poly) alkylene oxide, or reacting the (poly) alkylene oxide with an amino group. It can be formed by reacting a compound to which the atomic group is bonded. Examples of the atomic group that reacts with the amino group include atomic groups similar to those 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 having 2 to 2 carbon atoms. 8 alkylene oxides can be mentioned. Of these, an alkylene oxide having 2 to 4 carbon atoms 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 the atomic group that reacts with the amino group is bonded to the above (poly) alkylene oxide include methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (poly) propylene glycol (meth) acrylate, and methoxy ( Examples thereof include poly) ethylene glycol maleate and methoxy (poly) ethylene glycol (poly) propylene glycol maleate. One of these may be used, or two or more thereof may be used in combination.

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

When the polyamine compound has an oxyalkylene group-containing side chain, it is preferable that the oxyalkylene group-containing side chain is bonded to 10 to 100% of the nitrogen atoms of the polyamine compound. It is more preferably 30 to 100%, and even 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 and 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, 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, and propylene glycol monobutyl ether and their derivatives, and water, alcohol-based, hydrocarbon-based, and ester-based. Is preferable, and water, methanol, ethanol, isopropanol, cyclohexane, ethylene glycol, ethylene glycol monobutyl ether, and ethyl acetate are particularly preferable.

A catalyst may be used in the reaction between the unsubstituted polyamine compound and the compound for introducing a side chain in order to promote the reaction, and 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 can be used.
For other reaction conditions, Japanese Patent No. 4436921 and Japanese Patent Application Laid-Open No. 2008-230865 can be referred to.

At least one compound selected from the group consisting of (I) to (V) contained in the shrinkage reducing agent for hydraulic materials preferably satisfies the following conditions (1).
(1) A 15-stroke flow 10 minutes after the start of kneading the JASS 5 M402 compliant mortar composition to which the compound was added at a solid content concentration of 0.1% and the JASS 5 M402 compliant mortar containing no such compound. Ratio of values: (15 strokes flow value of the compound-containing mortar composition) / (15 stroke flow value of the mortar not containing the compound) × 100 is 120 or less It means that the flow value of the object is not too high. When the compound contained in the shrinkage reducing agent for hydraulic materials has such a predetermined dispersion performance, the shrinkage reducing performance is more excellent.
The JASS 5 M402 compliant mortar is described in Examples described later.

If the ratio of the 15-stroke flow value of the mortar composition containing the compound of (1) at a solid content concentration of 0.1% to the 15-stroke flow value of the mortar not containing the compound is 120 or less, the compound. Is not too high in performance for improving the flow value, but 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) contained in the shrinkage reducing agent for hydraulic materials also satisfies the following condition (2).
(2) 15 stroke flow value 2 hours after the start of kneading of the JASS 5 M402 compliant mortar composition to which the compound was added at a solid content concentration of 0.1% with respect to the JASS 5 M402 compliant mortar containing the compound. Ratio to the ratio of the 15-stroke flow value 10 minutes after the start of kneading: (ratio of the 15-stroke flow value after 2 hours) / (ratio of the 15-stroke flow value after 10 minutes) × 100 is 110 Hereinafter, the condition (2) above means that the ability 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 materials has such a predetermined dispersion performance, the shrinkage reducing performance is more excellent.

The ratio of the 15-stroke flow value 2 hours after the start of kneading of the mortar composition containing the compound at a solid content concentration of 0.1% to the mortar containing the compound in (2), that is, (containing the compound). The ratio of the value of 15 strokes flow value after 2 hours of the mortar composition / (15 stroke flow value after 2 hours of the mortar containing no compound) and the 15 stroke flow value 10 minutes after the start of kneading, that is, , (15 strokes flow value after 10 minutes of the compound-containing mortar composition) / (15 stroke flow value after 10 minutes of the mortar without the compound) × 100 is 110 or less. The compound does not have too high a performance for improving 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-based water reducing agent)
The polycarboxylic acid-based water reducing agent contained in the admixture material composition of the present invention is derived from the structural unit (a) derived from the unsaturated carboxylic acid-based monomer (A) and the unsaturated polyalkylene glycol-based monomer (B). It contains a copolymer having the structural unit (b) of (hereinafter, also referred to as a polycarboxylic acid-based copolymer).

The unsaturated carboxylic acid-based monomer (A) (hereinafter, also referred to as a monomer (A)) has an unsaturated double bond (carbon-carbon double bond) and a carboxy group and / or a carboxylic acid base. The monomer is not particularly limited as long as it contains a monomer.

Here, the term "containing a carboxy group and / or a carboxylic acid base" means that one group represented by -COMM (M represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group) is contained in one molecule. It means having more than one. Examples of the metal atom include alkali metals such as sodium, lithium, potassium, rubidium and cesium; alkaline earth metals such as magnesium, calcium, strontium and barium; aluminum and iron. The organic amine group includes an alkanolamine group such as a monoethanolamine group, a diethanolamine group and a triethanolamine group; an alkylamine group such as a monoethylamine group, a diethylamine group and a triethylamine group; and a polyamine such as an ethylenediamine group and a triethylenediamine group. The group etc. can be mentioned. Among these, the carboxylic acid base is more preferably an ammonium salt, a sodium salt or a potassium salt, and further preferably a sodium salt.

As the unsaturated carboxylic acid-based monomer (A), the unsaturated monocarboxylic acid-based 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 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 alcohol or amine. And the half ester of the unsaturated dicarboxylic acids; the half ester of the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 additional moles of these glycols and the like can be mentioned.
Examples of the unsaturated dicarboxylic acid-based monomer having two carboxy groups (or carboxylic acid bases) in one molecule include maleic anhydride, itaconic acid, citraconic acid, fumaric acid, or metal salts, ammonium salts, and organic amines thereof. Examples thereof include salts (organic ammonium salts), and examples of these anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
As the unsaturated carboxylic acid-based monomer, an unsaturated monocarboxylic acid-based monomer is preferable. More preferably, it is acrylic acid or methacrylic acid.

The unsaturated polyalkylene glycol-based monomer (B) (hereinafter, also referred to as monomer (B)) has the following formula (20);

(In the formula, R ²⁶ , R ²⁷ and R ²⁸ represent the same or different hydrogen atom or methyl group. R ²⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (R ³⁰ O) is the same or different and represents an oxyalkylene group. S represents the average number of moles of the oxyalkylene group added, and y represents a number of 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 preferably 2 to 18, preferably 2 to 8, and more preferably 2 to 4. Further, any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like can be used by any of random addition, block addition, alternating addition and the like. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group contains an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, and 90 mol% or more. It is more preferably an oxyethylene group.

In the above formula (20), it is appropriate that the average number of moles of oxyalkylene group added is 1 to 500. The larger the average number of moles added, the more hydrophilic the obtained polymer tends to be, and the more the dispersion performance tends to be improved. If it is 500 or less, it is possible to suppress the decrease in copolymerization reactivity. The average number of moles added is preferably 2 to 500, more preferably 5 to 500, further 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 hydrogen atoms or methyl groups. 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 radically polymerizable unsaturated bond. It is preferable not to use an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), a phenyl group having 6 to 30 carbon atoms, an alkylphenyl group, a phenylalkyl group, or a (alkyl) phenyl group. An aromatic group having a benzene ring such as a phenyl group or a naphthyl group substituted with is preferable, but as the number of carbon atoms of the hydrocarbon group increases, the hydrophobicity increases and the dispersibility decreases, so that R ²⁹ When is a hydrocarbon group, the number of carbon atoms is preferably 1 to 22, more preferably 1 to 18, further preferably 1 to 12, and particularly preferably 1 to 4. The 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, z represents 0 or 1, but when z is 0, the monomer (B) becomes an ether-based monomer. In this case, y is preferably 2. Further, in this case, it is more preferable that ^{R 28 is a methyl group.}
When z is 1, the monomer (B) is an ester-based monomer, and in this case, y is preferably 0. Further, in this case, R ²⁸ is more preferably a hydrogen atom or a methyl group, and even more preferably R ²⁸ is a methyl group.
Examples of the compound in which z in the above formula (20) is 0 and R ²⁹ is a hydrogen atom as the monomer (B) include (poly) ethylene glycol allyl ether, (poly) ethylene glycol metalyl ether, and (poly). ) Ethylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol metallic ether, (poly) ethylene (poly) propylene glycol 3-methyl- 3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly) ethylene (poly) butylene glycol metallic ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, etc. Can be mentioned.

Examples of the monomer (B) having z of 0 in the above formula (20) and R ²⁹ being a hydrocarbon group having 1 to 30 carbon atoms include methoxy (poly) ethylene glycol allyl ether and methoxy. (Poly) ethylene glycol metalyl ether, methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) propylene glycol metalyl 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 metallic ether, methoxy (poly) Examples thereof include ethylene (poly) butylene glycol 3-methyl-3-butenyl ether.

As the monomer (B), z in the above formula (20) is 1, and the ^{compound in which R 29} is a hydrogen atom is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono ( Meta) 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 (meth) ) Acrylate, (poly) alkylene glycol (meth) acrylate such as polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate can be mentioned.

As the monomer (B), z in the above formula (20) is 1, and R ²⁹ is a hydrocarbon group having 1 to 30 carbon atoms. Examples of the compound are methoxypolyethylene glycol mono (meth) acrylate and methoxy. Polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol polybutylene glycol mono (meth) acrylate, methoxypolyethylene glycol polybutylene glycol mono (meth) ) Acrylic, methoxypolyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxypolybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol polypropylene glycol Mono (meth) acrylate, ethoxypolyethylene glycol polybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol polybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, etc. Examples thereof include alkoxypolyalkylene glycol (meth) acrylate having a value of 1 to 30.

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

If the copolymer contained in the polycarboxylic acid-based water reducing agent has structural units (a) and (b), other monomers other than the above-mentioned 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 can be copolymerized with the monomers (A) and (B), and for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. Diesters of unsaturated dicarboxylic acids such as and alcohols having 1 to 30 carbon atoms; diamides of unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; the alcohols and amines have 2 to 18 carbon atoms. Diesters of alkyl (poly) alkylene glycol to which 1 to 300 mol of the alkylene oxide is added and the unsaturated dicarboxylic acids; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or the number of moles of these glycols added. Diesters with 2 to 300 polyalkylene glycols; unsaturated with methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methylcrotonate, ethylcrotonate, propylcrotonate, etc. Esters of saturated monocarboxylic acids and alcohols with 1 to 30 carbon atoms; halfamides of maleamic acid and glycols with 2 to 18 carbon atoms or polyalkylene glycols with 2 to 300 additional 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 Di (meth) acrylates; Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, trimethylpropandi (meth) acrylate; triethylene glycol dimalate, polyethylene glycol (Poly) alkylene glycol dimalates such as zimalate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2 -Hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyl oxysulfobenzoate, 4- (meth) acryloxibutyl sulfonate, (meth) acrylamide methyl Unsaturated sulfonic acids such as sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organics. Amine salts (organic ammonium salts); amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms; styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, etc. Vinyl aromatics; alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate. Classes: Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chlor-1,3-butadiene, etc.

Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; unsaturated cyanide such as (meth) acrylonitrile and α-chloroacrylonitrile Classes; 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 (meth) acrylate, vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth) allyl ether, etc. Allyls; polydimethylsiloxane propylaminomale amidoic acid, polydimethylsiloxane aminopropylene aminomale amidoic acid, polydimethylsiloxane-bis- (propylaminomale amidoic acid), polydimethylsiloxane-bis- (dipropylene aminomale amidoic acid) , Polydimethylsiloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis Examples thereof include siloxane derivatives such as − (1-propyl-3-methacrylate).

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

In the polycarboxylic acid-based copolymer, the ratio 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. It is more preferably 0 to 30% by mass, and further preferably 0 to 20% by mass.

The polycarboxylic acid-based copolymer preferably has a weight average molecular weight of 1000 to 1000000. More preferably, it is 2500 to 500000, and when the weight average molecular weight is 2500 to 500000, the water reducing performance and the slump loss preventing ability of the copolymer can be made more sufficient. It is even more preferably 5000 to 250,000, and even more preferably 1000 to 100,000. The weight average molecular weight of the polycarboxylic acid-based copolymer can be measured by GPC under the measurement conditions described in Examples.

The production of the polycarboxylic acid-based copolymer is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component are as described above. The content ratios of the monomers (A), (B) and (C) with respect to 100% by mass of the monomer component are the structural units (a), (b) and (c) with respect to 100% by mass of all the structural units described above. ) Is the same.

A chain transfer agent is usually used in the polymerization reaction to obtain a polymer. Examples of the chain transfer agent include thiol-based chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thioapple acid, and 2-mercaptoethanesulfonic acid; secondary alcohols such as isopropyl alcohol; sub Phosphoric acid, hypophosphate and its salts (sodium hypophosphate, potassium hypophosphate, etc.), sulfite, hydrogen sulfite, dithionic acid, metabisulfite and its salts (sodium bisulfite, sodium bisulfite, subsulfur) Examples thereof include lower oxides of (sodium dithionate, sodium metabisulfite, etc.) and hydrophilic chain transfer agents such as salts thereof.

As the chain transfer agent, a hydrophobic chain transfer agent can also be used. Examples of the hydrophobic chain transfer agent include butane thiol, octane thiol, decane thiol, dodecane thiol, hexadecane thiol, octadecane thiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, and octyl 3-mercaptopropionate. A thiol-based chain transfer agent having the above hydrocarbon groups 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, based on 100 mol of the total amount of the monomer components. It is in mol%, more preferably 1.5 to 3.0 mol%.

The above polymerization reaction can be carried out by a method such as solution polymerization or bulk polymerization using a radical polymerization initiator, if necessary. The solution polymerization can be carried out in a batch system, a continuous system, or a combination thereof, and examples of the solvent used in this case include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; benzene, toluene, and the like. 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 can be mentioned. Above all, it is preferable to polymerize by the aqueous solution polymerization method.

Among the above solution polymerizations, it is preferable to use a water-soluble radical polymerization initiator in the aqueous solution polymerization because it is not necessary to remove the insoluble component after the polymerization. For example, persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; hydrogen peroxide; azoamidin compounds such as 2,2'-azobis-2-methylpropion amidine hydrochloride, 2,2'-azobis-2- Cyclic azoamidine compounds such as (2-imidazolin-2-yl) propane hydrochloride, azonitrile compounds such as 2-carbamoyl azoisobutyronitrile, 2,4'-azobis {2-methyl-N- [2- (1- (1-) Examples thereof include azoamide compounds such as hydroxybutyl)] propionamide}, and water-soluble azo-based initiators such as macroazo compounds such as esters of 4,4'-azobis (4-cyanovaleric acid) and (alkoxy) polyethylene glycol. One or more of these can be used. Of these, hydrogen peroxide and persulfate-based initiators 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, still more preferably, based on 100 mol of the total amount of the 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 sulfites such as sodium hydrogen sulfite, Fe (II) salts such as metadibisulfite, sodium hypophosphite, and molle salts, sodium hydroxymethanesulfite 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, and examples of the organic reducing agent include L-ascorbic acid (salt), L-ascorbic acid ester, erythorbic acid (salt), and erythorbic acid ester. It can be preferably used. 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, but 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. It is more preferably 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, solvent, polymerization initiator, and chain transfer agent used, but the polymerization temperature is preferably 0 ° C. or higher. It is preferably 150 ° C. or lower. It is more preferably 30 ° C. or higher, and even more preferably 50 ° C. or higher. Further, it is more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

The ratio of the shrinkage reducing agent for hydraulic materials contained in the admixture material composition of the present invention is preferably 10 to 99.9% by mass with respect to 100% by mass of the admixture material composition. It is more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass.

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

The admixture material composition of the present invention can be suitably used as a cement additive. The cement additive containing the admixture material composition of the present invention will have the effect of reducing the shrinkage that occurs when the hydraulic material dries, reducing or preventing cracking of the cured product, improving the filling property, and warping. It can be used mainly for prevention, prevention of peeling, etc., and can be suitably used for hydraulic materials described later.
The mixed material composition may contain other components, if necessary, in addition to a shrinkage reducing agent for hydraulic materials and a polycarboxylic acid-based water reducing agent.
As other components, the same components as 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 containing a shrinkage reducing agent for a hydraulic material, a polycarboxylic acid-based water reducing agent, and a hydraulic material, and the shrinkage reducing agents for a hydraulic material are described in the following (I) to (I). It is also a hydraulic material composition containing at least one compound selected from the group consisting of V).
(I):
The following formula (1);

(In the formula (1), R ^{1 to} R ³ represent the same or different hydrogen atom or methyl group. R ⁴ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. P represents a number from 0 to 5, q is a number of 0 or 1, and n is an average addition molar of an oxyalkylene group. The structural unit (I) represented by (a number of 7 to 300) representing a number and the following formula (2);

(In formula (2), R ^{6 to} R ⁸ represent the same or different hydrogen atom, methyl group _{or-(CH 2} ) _m COOZ'group, where m is an integer of 0 to 2. , Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). A polymer having II), in which the ratio of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of the total structural unit, and the ratio of the structural unit (II). However, the polymer (II): which is 10 to 59 mol% with respect to 100 mol% of the total structural unit:
The following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In the 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. Representing 18 oxyalkylene groups. 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, 0 to 2000, and f + g = 1 to 2000. Y represents the residue of the compound having active hydrogen. K and l are the same or different, 0 to 6. However, k + l is 1 or more.) A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer, the ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer, and the polymer is an unsaturated carboxylic acid-based simple substance. Polymer (III) in which the proportion of structural units derived from the weight is 0.1 to 12% by mass with respect to 100% by mass of all structural units, and the weight average molecular weight of the polyether compound is 1500 to 50,000. :
A copolymer having a structure in which a polymer chain (A) derived from an ethylenically unsaturated monomer component and a terminal of a (poly) alkylene glycol chain (B) are bonded via a bonding site (X). The ethylenically unsaturated monomer contains an unsaturated anionic monomer, and the copolymer has a structural unit derived from the unsaturated anionic monomer in an amount of 1 mol of a (poly) alkylene glycol chain. On the other hand, the weight average molecular weight of the (poly) alkylene glycol which is 1 to 30 mol and forms the (poly) alkylene glycol chain is 1500 to 50,000, and the (poly) alkylene glycol-based block copolymer (IV):
A polyalkylene glycol compound in which an organic residue exhibiting an adsorptive ability to 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. The polyalkylene glycol compound has a weight average molecular weight of 1500 to 50,000 of the polyalkylene glycol forming the polyalkylene glycol chain, and the organic residues are a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, and a sub. 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, wherein the polyamine compound has a structural unit derived from an unsubstituted polyamine compound and a structural unit derived from an unsaturated carboxylic acid-based monomer, and the unsaturated carboxylic acid-based compound. A polyamine compound having an acid group-containing side chain in which the proportion of structural units derived from the monomer 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 above-mentioned 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 material composition. Is preferable.
Further, the hydraulic material composition preferably further contains water.

The method for producing the composition containing the hydraulic material-based shrinkage reducing agent, polycarboxylic acid-based water reducing agent, 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, the hydraulic material and water by various commonly used methods described in JP-A-2008-503432 and JP-A-2008-512268 can be used. Examples of the commonly used method include the methods listed below, and two or more of these methods may be used in combination.
(A) A method of diluting a shrinkage reducing agent and a polycarboxylic acid-based water reducing agent with water and mixing them with a hydraulic material to produce a hydraulic material composition (b) A shrinkage reducing agent and a polycarboxylic acid-based water reducing agent. A method of producing a hydraulic material composition by mixing it with a hydraulic material after making it into a powder and adding water to the obtained mixture (c) A shrinkage reducing agent and a polycarboxylic acid-based water reducing agent during the production of the hydraulic material. Method of adding water to produce 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, water As a method of adding a shrinkage reducing agent at the time of manufacturing a rigid material, a method of adding a crushing aid or a shrinkage reducing agent at the same time as the crushing 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 manufacturing a hydraulic material.

The water-hardening material to which the shrinkage reducing agent for water-hardening material and the polycarboxylic acid-based water-reducing agent of the present invention is used is not particularly limited as long as it has water-hardness or latent water-hardness, and is, for example, ordinary Portland cement. Portland cement such as early-strength Portland cement, moderate heat Portland cement, low heat Portland cement, silica cement, fly ash cement, blast furnace cement, alumina cement, belite high content cement, various mixed cements; tricalcium silicate, dicalcium silicate, Constituent components of cement such as tricalcium aluminate and tetracalcium iron aluminate; fly ash having latent water hardness and the like can be mentioned. These may be used alone or in combination of two or more. Among these, ordinary Portland cement is usually commonly used and can be preferably applied.

The amount of the shrinkage reducing agent for a hydraulic material used in the hydraulic material composition of the present invention is preferably 0.0001 to 10% by weight in terms of solid content with respect to the 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, the curing of the hydraulic material may be delayed. It is more preferably 0.001 to 5% by weight, still more preferably 0.005 to 3% by weight, and most preferably 0.01 to 1% by weight.

The amount of the polycarboxylic acid-based water reducing agent used in the hydraulic material composition of the present invention is preferably 0.001 to 10% by weight in terms of solid content with respect to the hydraulic material, for example. It is more preferably 0.01 to 5% by weight, still more preferably 0.05 to 3% by weight.

In the above hydraulic material composition, the blending ratio of the shrinkage reducing agent and the polycarboxylic acid-based water reducing agent (mass of the shrinkage reducing agent) / (mass of the water reducing agent) is 99.9 / 0.1 to 40/60. It is preferable to have. It is more preferably 99/1 to 50/50, further preferably 98/2 to 60/40, particularly preferably 98/2 to 65/35, and most preferably 97/3 to It is 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 mixture of various components may be insufficient and molding may not be possible or the strength may be lowered. If it exceeds 80% by weight, the strength of the cured product of the hydraulic material composition may be reduced. May decrease. It is more preferably 15 to 75% by weight, further preferably 20 to 70% by weight, and most preferably 25 to 65% by weight.

When the above-mentioned water-hard material composition is used as a mortar or concrete, the sand or stone to be blended in the water-hard material composition may be those used in conventionally known cement compositions, and is 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 crushing these rocks and slabs; lightweight fine aggregates and the like. The blending amount of sand may be the same as that of a conventionally known cement composition, and is not particularly limited. Further, the blending amount of the stone may be the same as that of the conventionally known cement composition, and is not particularly limited, but for example, the fine aggregate ratio is preferably 20 to 60% by volume. If it is less than 20% by volume, the concrete will be squeezed, and in concrete with a large slump, the coarse aggregate and the mortar component may be easily separated. If it exceeds 60% by volume, a large amount of unit cement and a unit amount of water are required, and the concrete may have poor fluidity. More preferably, it is 30 to 50% by volume.

Other materials may be blended in the hydraulic material composition, if necessary. As the other material, the same material as the conventionally known cement composition can be used, and is not particularly limited. For example, other water reducing agents other than the above polycarboxylic acid-based water reducing agent, AE agent (air entraining agent). , Antifoaming agent, hardening accelerator, retarding agent, rust preventive, expanding material, silica powder, fibrous material such as steel fiber, glass fiber and the like. The blending amount of these materials may be the same as that of the conventionally known hydraulic material composition, and is not particularly limited.

When the hydraulic material composition contains other water reducing agents, the content of the other water reducing agents is preferably 0.001 to 10 parts by weight in terms of solid content with respect to 100 parts by weight of the hydraulic material. .. It is more preferably 0.01 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight.

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

From the viewpoint of making the hydraulic material composition of the present invention excellent in freeze-thaw resistance, it is preferable that the hydraulic material composition contains fine bubbles, and an air entrainment agent (AE agent) may be contained. preferable.
When the hydraulic material composition of the present invention contains an AE agent, the content of the AE agent is preferably 0.002 parts by weight or more with respect to 100 parts by weight of the hydraulic material. By including it in such a ratio, the performance of the AE agent such as improvement of freeze-thaw resistance can be effectively exhibited. The content of the AE agent is more preferably 0.0025 parts by weight or more, still more 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 a part by weight. The content of the AE agent is usually preferably 0.1 parts by weight or less with respect to 100 parts by weight of the hydraulic material. More preferably, it is 0.05 parts by weight or less, and even more preferably 0.04 parts by weight or less.

When the hydraulic material composition of the present invention contains an AE agent, the mixing ratio of the hydraulic material shrinkage reducing agent 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. It is 2 to 90/10.
In the hydraulic material composition containing the shrinkage reducing agent for hydraulic material, the hydraulic material and the AE agent of the present invention, the content of the AE agent is 0.002 with respect to 100 parts by mass of the hydraulic material. A hydraulic material composition having a mass ratio of 99.98 / 0.02 to 80/20 between a shrinkage reducing agent for a hydraulic material and an AE agent, which is more than a part by weight, is also one of the present inventions.

The AE agent contained in the water-hard material composition of the present invention is not particularly limited as long as it functions as an AE agent, and is, for example, resin soap, saturated or unsaturated fatty acid or a salt thereof, sodium hydroxystearate, lauryl sulfate. , ABS (alkylbenzene sulfonate), LAS (linear alkylbenzene sulfonate), alkylnaphthalene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or Examples thereof include the salt, polyoxyethylene alkyl (phenyl) ether phosphate ester or salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate, polyoxyethylene sorbitan oleate and the like.
Of these, resin soap, saturated or unsaturated fatty acids or salts thereof, ABS (alkylbenzene sulfonate), LAS (linear alkylbenzene sulfonate), polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) Ether sulfate ester or a salt thereof, polyoxyethylene sorbitan oleate is preferable, and resin soap, ABS (alkylbenzene sulfonate), LAS (linear alkylbenzene sulfonate), polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (Phenyl) ether sulfate ester or a salt thereof, polyoxyethylene sorbitan oleate is particularly preferable.

From the viewpoint of making the hydraulic material composition of the present invention excellent in freeze-thaw resistance, it is preferable that the bubbles present in the hydraulic material composition are fine, and with the addition of a shrinkage reducing agent or the like. It is preferable to include a defoaming agent in order to eliminate large bubbles contained in the composition.
When the hydraulic material composition of the present invention contains a defoaming agent, the blending ratio (mass of the shrinkage reducing agent) / (mass of the defoaming agent) of the shrinkage reducing agent for the hydraulic material and the defoaming 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, further preferably 99.96 / 0.04 to 90/10, and particularly preferably 99.95 / 0. It is 05 to 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 that purpose, a shrinkage reducing agent with respect to the hydraulic material. It is preferable to use a shrinkage reducing agent such that the bubble spacing coefficient of the mortar composition to which 0.7% by mass is added by an air void analyzer is 350 μm or less. Further, by using a defoaming agent, it is possible to eliminate large bubbles contained in the composition with the addition of a shrinkage reducing agent or the like, so that the freeze-thaw resistance of the hydraulic material composition can be further improved. ..
A composition for a hydraulic material containing such a shrinkage reducing agent and a defoaming agent in a predetermined ratio, that is, a composition for a hydraulic material containing a shrinkage reducing agent for a hydraulic material and a defoaming agent. , The mixing ratio of the shrinkage reducing agent for hydraulic materials and the defoaming agent in the composition for hydraulic materials (mass of shrinkage reducing agent for hydraulic materials) / (mass of defoaming agent) is 99.99 / 0. It is 01 to 85/15, and is characterized in that the bubble spacing coefficient of the mortar composition obtained by adding 0.7% by mass of the shrinkage reducing agent for hydraulic material to the hydraulic material can be adjusted to 350 μm or less by an air void analyzer. The composition for hydraulic materials is also one of the present inventions.
The composition for hydraulic materials of the present invention preferably further contains an AE agent. When the composition for hydraulic material contains an AE agent in addition to the defoaming agent, the hydraulic material composition obtained by adding the composition for hydraulic material to the hydraulic material has more excellent freeze-thaw resistance. It will be. When the composition for hydraulic material of the present invention contains an AE agent, the content of the AE agent is preferably the same as the content when the above-mentioned hydraulic material composition contains an AE agent.
That is, the composition for hydraulic materials of the present invention further contains an AE agent, and the blending ratio of the shrinkage reducing agent for hydraulic materials and the AE agent in the composition for hydraulic materials (the shrinkage reducing agent for hydraulic materials). The mass) / (mass of the AE agent) of 99.98 / 0.02 to 80/20 is one of the preferred forms of the composition for hydraulic materials of the present invention.

The defoaming agent contained in the hydraulic material composition of the present invention is not particularly limited as long as it functions as a defoaming agent, but for example, one of the defoaming agents exemplified in the following (1) to (10). Species or two or more species can be used.
(1) Mineral oil-based defoaming agent: kerosene, liquid paraffin, etc.
(2) Oil-based antifoaming agents: animal and vegetable oils, sesame oils, castor oils, alkylene oxide adducts thereof, etc.
(3) Fatty acid-based antifoaming agent: oleic acid, stearic acid, these alkylene oxide adducts and the like.
(4) Fatty acid ester antifoaming agent: glycerin monolithinolate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.
(5) Oxyalkylene-based defoaming agent: Polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as -2-ethylhexyl ether and oxyethyleneoxypropylene adduct to higher alcohols having 12 to 14 carbon atoms; (poly) such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether. Oxyalkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexine-2,5-diol, 3-methyl- Acetylene ethers obtained by addition-polymerizing alkylene oxide to acetylene alcohol such as 1-butin-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleic acid ester, diethylene glycol lauric acid ester, and ethylene glycol distearate ester; poly (Poly) oxyalkylene sorbitan fatty acid esters such as oxyethylene sorbitan monolauric acid ester and polyoxyethylene sorbitan trioleic acid ester; (poly) oxyalkylene such as polyoxypropylene methyl ether sulfate sodium and polyoxyethylene dodecylphenol ether sulfate sodium Alkyl (aryl) ether sulfate ester salts; (poly) oxyalkylene alkyl phosphates such as (poly) oxyethylene stearyl phosphate; (poly) oxyalkylene alkyl amines such as polyoxyethylene laurylamine; polyoxyalkylene Amid; etc.
(6) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, 2-ethylhexyl alcohol, acetylene alcohol, glycols and the like.
(7) Amide-based antifoaming agent: acrylate polyamine and the like.
(8) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.
(9) Metal soap defoaming agent: aluminum stearate, calcium oleate, etc.
(10) Silicone-based defoaming 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), and defoaming agent, the hydraulic material composition of the present invention reduces shrinkage for hydraulic materials. It can also be said that the composition for a hydraulic material 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, a polycarboxylic acid-based water reducing agent, and other materials is also one of the present inventions.
When the composition for a hydraulic material of the present invention contains an AE agent or an antifoaming agent, the preferable blending ratio of the shrinkage reducing agent for a hydraulic material and those agents is the same as the preferable blending ratio in the above hydraulic material composition. Is.

The composition for hydraulic materials of the present invention is characterized in that the bubble spacing coefficient of a mortar composition obtained by adding 0.7% by mass of a shrinkage reducing agent for hydraulic materials to cement can be adjusted to 350 μm or less by an air void analyzer. It is preferable that the composition is to be used. In order to improve the freeze-thaw resistance of the composition for hydraulic materials, 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, and 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, further preferably 300 μm or less, and particularly preferably 280 μm or less. The bubble spacing coefficient is usually 120 μm or more.

Since the admixture material composition of the present invention has the above-mentioned structure and can sufficiently exhibit both shrinkage reduction and the fluidity of the cement composition, it can be suitably used for a hydraulic material composition or the like. ..

Hereinafter, the present invention will be described in more detail with reference to Examples, but 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)>
Equipment: Waters Alliance (2695)
Analysis software: Waters, Emper Professional + GPC option used Column: Tosoh Co., Ltd., TSKguardcorensα + TSKgelα5000 + α4000 + α3000
Detectors: Differential Refractometer (RI) Detector (Waters 2414), Multi-Wavelength Visible Ultraviolet (PDA) Detector (Waters 2996)
Eluent: 93.98 g of boric acid and 30.4 g of sodium hydroxide dissolved in a mixed solvent of 15076 g of water and 3800 g of acetonitrile Standard material for calibration curve preparation: Polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic formula based on the Mp value and elution time of the above 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 1 900.3 parts of water is charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and nitrogen is mixed in the reaction device under stirring. It was replaced and heated to 92 ° C. in a nitrogen atmosphere. 128.0 parts of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added 23), 5.6 parts of methacrylic acid, 32.0 parts of water, 0.43 parts of 30% aqueous sodium hydroxide solution, and 3-mercapto as a chain transfer agent. A monomer aqueous solution containing 0.71 part of propionic acid was added dropwise to the reaction vessel over 4 hours, and 42.0 parts of 1.5% ammonium persulfate was added dropwise to the reaction vessel over 5 hours. The temperature was maintained at 92 ° C. for another 1 hour to complete the polymerization reaction, and the polymer aqueous solution was neutralized to pH 7.0 with a 30% sodium hydroxide aqueous solution to have an acid content of 36.1 mol% and a weight average molecular weight of 26000. (Polymer 1) was obtained. The ratio of the amount of acid is the ratio of the monomer having an acid group calculated from the number of moles of the monomer used for producing the polymer.

(Production Example 2) Production of Polymer 2 Monomer polyethylene glycol monoacrylate (average number of moles of ethylene oxide added 23) 123.8 parts, 8.9 parts methacrylic acid, 30.9 parts water, 30% aqueous sodium hydroxide solution 0. A polymer aqueous solution having an acid content of 48.2 mol% and a weight average molecular weight of 24,000 by the same method as in Production Example 1 except that a monomer aqueous solution in which 69 parts and 0.70 parts of 3-mercaptopropionic acid were mixed as a chain transfer agent was used. (Polymer 2) was obtained.

(Production Example 3) Production of polymer 3 69.3 parts of water is charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and nitrogen is inside the reaction device under stirring. It was replaced and heated to 92 ° C. in 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 parts of 30% aqueous sodium hydroxide solution and 3-mercapto as a chain transfer agent. A polymer aqueous solution (polymer 3) having an acid content of 45.2 mol% and a weight average molecular weight of 11000 was obtained by the same method as in Production Example 1 except that an aqueous monomer solution containing 1.87 parts of propionic acid was used.

(Production Example 4) Production of polymer 4 91.3 parts of water is charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and nitrogen is mixed in the reaction device under stirring. It was replaced and heated to 80 ° C. in a nitrogen atmosphere. 123.3 parts of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added 23), 6.7 parts of methacrylic acid, 3.4 parts of hydroxyethyl acrylate, 30.8 parts of water, 0.60 parts of 30% aqueous sodium hydroxide solution. And a polymer aqueous solution (heavy) having an acid content of 36.1 mol% and a weight average molecular weight of 26500 by the same method as in Production Example 1 except that a monomer aqueous solution containing 0.91 part of 3-mercaptopropionic acid was used as a chain transfer agent. A coalescence 4) was obtained.

(Production Example 5) Production of Polymer 5 91.3 parts of water is charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and nitrogen is mixed in the reaction device under stirring. It was replaced and heated to 80 ° C. in a nitrogen atmosphere. 123.3 parts of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added 23), 7.7 parts of methacrylic acid, 2.0 parts of hydroxypropyl acrylate, 30.8 parts of water, 0.60 parts of 30% aqueous sodium hydroxide solution And a polymer aqueous solution (heavy) having an acid content of 41.9 mol% and a weight average molecular weight of 21000 by the same method as in Production Example 1 except that a monomer aqueous solution in which 0.91 part of 3-mercaptopropionic acid was mixed was used as a chain transfer agent. A coalescence 5) was obtained.

(Production Example 6) Production of Polymer 6 In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 200.0 parts of polyethylene glycol having a weight average molecular weight of 4500 is charged and 120 parts under a nitrogen stream. It was heated to ± 5 ° C. and melted. 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 Nippon Oil & Fats Co., Ltd., di-t-butyl peroxide) were separately added for 1 hour. After that, stirring was continued for 1 hour while keeping the temperature at 120 ± 5 ° C., heating was completed, 200.0 parts of water was added when the temperature was cooled to 80 ° C., and the pH was further increased with a 30% aqueous sodium hydroxide solution. It was neutralized to 7 to obtain a polymer aqueous solution (polymer 6) having a weight average molecular weight of 5000 and an acid content of 79.5 mol%.

(Production Example 7) Production of polymer 7 (1. Tosylation step)
In a glass reactor equipped with a stirrer, 100.86 parts of polyethylene glucol (PEG10000) having a weight average molecular weight of 10000, 4.576 g of tosyl chloride (TsCl), and 3.036 parts of triethylamine (Et ₃ N). , Dichloromethane (CH ₂ Cl ₂ ) was charged in 200.0 parts. After the reaction was carried out for 24 hours while stirring the inside of the reaction system, the salt was removed by filtration, and the filtrate was desolvated under reduced pressure to obtain both-terminal tosylates of PEG10000 (PEG10000-2OTs).
(2. Thioacetylation step)
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 carrying out the reaction for 24 hours while stirring the inside of the reaction system, the salt was removed by filtration, and the solvent was removed under reduced pressure to obtain a thioacetylated product having both ends of PEG10000 (PEG10000-2SAc).
(3. Hydrolysis step)
In a glass reactor equipped with a stirrer, 92.65 parts of the synthesized PEG10000-2SAc and 100.00 parts of methanol (MeOH) were charged to dissolve the PEG10000-2SAc, and a 1N aqueous solution of sodium hydroxide (NaOH) was added. After adding 25.00 parts and stirring for 10 minutes, 25.00 parts of 1N hydrochloric acid (HCl) was added and stirred for another 10 minutes, dichloromethane was added and extraction was performed, the organic layer was recovered, and the solvent was removed under reduced pressure. Was carried out to obtain PAG dithiol compound 1.
(4. Block polymerization step)
15.0 parts of ion-exchanged water was charged into a glass reactor equipped with a thermometer, agitator, dropping device, nitrogen introducer and reflux cooling device, the reactor was replaced with nitrogen under stirring, and the temperature was 80 ° C. in a nitrogen atmosphere. After the temperature was raised to 2.680 parts of methacrylic acid (MAA) and 10.720 parts of ion-exchanged water (PW), an aqueous solution (A) (acid aqueous solution) consisting of 10.720 parts was added dropwise over 4.0 hours to (A). At the same time as the dropping was started, an aqueous solution (B) (PAG thiol aqueous solution) consisting of 31.37 parts of PAG dithiol compound 1 and 62.74 parts of ion-exchanged water was added dropwise over 4.0 hours. Further, at the same time when (A) is started to be dropped, the azo initiator 2,2'-azobis-2-methylpropionamidine hydrochloride [2,2'-azobis (2-methylropionamide) dihydrochloride] (manufactured by Wako Pure Chemical Industries, Ltd.) V-50) An aqueous solution (C) consisting of 0.2830 parts and 8.843 parts of ion-exchanged water was added dropwise over 5.0 hours. Then, after maintaining the temperature at 80 ° C. for 1 hour, the polymer 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 10000. An aqueous copolymer solution (polymer 7) having 90.9 mol% of acid content having 5 mol of methacrylic acid chains 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)
In a glass reaction vessel equipped with a thermometer, a dropping device and a reflux condenser, 10.00 parts of dehydrated tetrahydrofuran (THF) was charged, stirred with a magnetic stirrer, and 1.00 parts of sodium hydride was dissolved while cooling with ice. I let you. After melting, 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 while cooling with ice, and the mixture was further stirred for about 5 minutes and then at 40 ° C. It was heated to. To this, 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. Then, a small amount of deionized water is added to treat the unreacted sodium hydride, and THF is further distilled off with an evaporator, the residue is added dropwise to 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. Here, 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 an internal temperature of 55 ° C. Then, 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 content of 66.7 mol%.

(Production Example 9) Production of Polymer 9 In a glass reaction vessel equipped with a thermometer, agitator, a dropping funnel, a nitrogen introduction tube and a reflux condenser, Epomin SP-200 (polyethylene imine having a number average molecular weight of 10000; Nippon Catalyst Co., Ltd.) (Manufactured) 123.7 parts were charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and the mixture was heated to 60 ° C. under a nitrogen atmosphere and stirred. To this, 11.81 parts of methyl acrylate was added dropwise over 0.5 hours, 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 an aqueous NaOH solution adjusted to 30 wt% and 340.5 parts of pure water were added, and then the temperature was raised to 70 ° C., and methyl acrylate was hydrolyzed over 1 hour. After the completion of hydrolysis, the temperature is lowered to 20 ° C. or lower, 37.99 parts of acetic acid is added, and the pH is adjusted to 8.4 to adjust the weight average molecular weight to 10450 and the acid content to 91.7 mol%. 9) was obtained.

(Production Example 10) Production of polymer 10 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser, Epomin SP-200 (polyethyleneimine having a number average molecular weight of 10000; Nippon Catalyst Co., Ltd.) (Manufactured by) A polymer aqueous solution (polymer 10) having a weight average molecular weight of 10300 and an acid content of 87.9 mol% was obtained by the same method 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 An aqueous comparative polymer solution (comparative polymer 1) having an acid content of 61.3 mol% was obtained in the same manner as in Reference Example 4 of Japanese Patent No. 3179022.

(Comparative Production Example 2) Production of Comparative Polymer 2 In a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, 112.5 parts of polyethylene glycol having a weight average molecular weight of 6000 and 28.7 parts of acrylic acid A comparative polymer aqueous solution (comparative polymer 2) having an acid content of 95.5 mol% was obtained by the same method as in Production Example 6 except that 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 (PEG1000) having an average addition molar number of 25 ethylene oxide, 13.75 parts of tosyl chloride (TsCl), _{and 9 parts of triethylamine (Et 3} N). Tosylated products of PEG1000 (PEG1000-OTs) were 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 step)
The same method as 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. A thioacetylated product of PEG1000 (PEG1000-SAc) was obtained.
(3. Hydrolysis step)
PAG was carried out in the same manner as in the hydrolysis step of Production Example 7, except that 43.572 parts of the 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 step)
121.30 parts of methacrylic acid, 18.806 parts of 30% sodium hydroxide aqueous solution and 435.2 parts of ion-exchanged water were added to the acid aqueous solution, and 37.50 parts of PAG dithiol compound 2 and 65.54 parts of ion-exchanged water were added to the PAG aqueous solution. An acid amount 97 having 20 mol of methacrylic acid chains at both ends with respect to 1 mol of polyethylene glycol having a weight average molecular weight of 6430 and an average addition molar number of 25 ethylene oxide by the same method as 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 is charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, and the mixture is stirred. The inside of the reaction vessel was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. Next, 1668 parts of methoxypolyethylene glycol monomethacrylic acid ester (average number of moles of ethylene oxide added: 25), 332 parts of methacrylic acid and 500 parts of water were mixed, and 16.7 parts of mercaptopropionic acid was uniformly added as a chain transfer agent. An aqueous monomer solution was prepared by mixing. 184 parts of each of the monomer aqueous solution and the 10% ammonium persulfate aqueous solution was added dropwise in 4 hours, and 46 parts of the 10% ammonium persulfate aqueous solution was further added dropwise in 1 hour after the completion of the addition. After that, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and the mixture was 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) 72.26 parts of ion-exchanged water, 3-methyl- in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, and a recirculation cooler. 127.74 parts of unsaturated alcohol to which 50 mol of ethylene oxide was added to 3-butene-1-ol was charged, the temperature was raised to 65 ° C., and then 0.38 part of a 30% aqueous solution of hydrogen peroxide was added to acrylic acid. 19.83 parts of a 40% aqueous acid solution was added dropwise over 3 hours, 0.35 parts of 3-mercaptopropionic acid was added dropwise over 3 hours, and 6.99 parts of a 2.1% aqueous solution of L-ascorbic acid was added dropwise over 3.5 hours. Then, the temperature was continuously maintained at 65 ° C. for 60 minutes to complete the polymerization reaction, the temperature was lowered to 50 ° C. or lower, and neutralized with 79.12 parts of a 5.0% aqueous sodium hydroxide solution from pH 4 to pH 7. Then, an aqueous polymer 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 JASS 5 M402 compliant mortar was prepared with the following formulation, and the above polymers 1 to 10, comparative polymers 1 to 3, and commercially available weight average molecular weight 1000 were prepared by the following 15-stroke flow and 0-stroke 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 10000 (SP-200: Comparative Polymer 6). Condition (1): (15 stroke flow value of the polymer-containing polymer composition) / (15 stroke flow value of the polymer not containing the compound) × 100, condition (2): (after 2 hours). The value of (ratio of 15-stroke flow value) / (ratio of 15-stroke flow value 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.
When the polymer (shrinkage reducing agent) was added to the JASS 5 M402 compliant mortar, it was added so that the total amount of water and the polymer was 225 g.
(I): Polycarboxylic acid-based polymer (II): Graft polymer (III): (Poly) alkylene glycol-based block copolymer (IV): Chelate PEG polymer (V): Polyamine-based polymer

<JASS 5 M402 compliant mortar>
Ordinary Portland cement (JIS R 5210 compliant product) 450g
Water (deionized water) 225 g
ISO Sand (Cement Association) 1350g
Defoamer (master air 404 (manufactured by BASF Japan) added) so that the amount of mortar air is ± 3% without shrinkage reducing agent (plain)
<Kneading of mortar composition>
The kneading of the mortar composition was carried out according to the method of JIS R5201-1997 Annex 2 as follows. 225 g of each polymer or shrinkage reducing agent and defoaming agent diluted with water so as to have a solid content of 0.1% or 1.0% with respect to 100 parts by weight of cement was charged into a kneading pot. 450 g of ordinary Portland cement was placed therein, and the mixture was immediately started at a low speed (rotation speed 140 ± 5 rpm, revolution speed 62 ± 10 rpm). Thirty seconds after the start-up, 1350 g of standard sand for cement strength test (specified in 5.1.3 of JIS R5201-1997 Annex 2) was added over 30 seconds. After the sand was added, the mixture was kneaded at a high speed (rotation speed 285 ± 10 rpm, revolution speed 125 ± 10 rpm) for another 30 seconds, and kneading was stopped for 90 seconds. The mortar attached to the kneading pot 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 rest, kneading was performed again at high speed for 60 seconds to complete the kneading.
After the kneading was completed, the mortar was taken out from the kneading pot and the amount of air was measured according to the method of JIS A1174-1978.
Further, 10 minutes after the kneading, the mortar was taken out from the kneading pot, and the mortar flow was measured according to the method of JIS R5201-1997 shown below. After measuring the air volume and the mortar flow value, the mortar was placed in a polybeaker having a capacity of 1000 ml, and the top of the container was covered with a wet cloth to prevent drying. In addition, the entire mortar was stirred about 10 times using a stainless steel spoon every hour from the start of kneading.
Two hours after kneading, the entire mortar was stirred about 10 times using a stainless steel spoon, and then a 15-stroke flow measurement was performed.

<Measurement of 0-stroke flow and 15-stroke flow of mortar composition>
The 0-stroke flow and 15-stroke flow measurements of the mortar composition were carried out as follows according to the method of JIS R5201-1997.
Twice the mortar on 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 position on a flow table wiped well with a dry cloth. Divide into and put in. Insert it to a height of 1/2, poke the entire surface 15 times with a thrust rod (diameter 20 ± 1 mm, length 200 mm), then insert mortar to the top of the flow cone, pierce the entire surface 15 times with a thrust rod, and there is a shortage. If there is, make up for it and smooth the surface. Then, the flow cone was removed directly above and the diameter of the spread mortar was measured and set to a 0-stroke flow value. After measuring the 0-stroke flow, the flow table was given a falling motion 15 times in 15 seconds, and then the diameter of the spread mortar was measured to obtain a 15-stroke flow value.
The diameter was measured in the direction recognized as the maximum diameter of the mortar after spreading and in the direction perpendicular to this, and the average value was taken as the flow value of 0 strokes and 15 strokes.

<Examples 1 to 12 and Comparative Examples 1 to 15: Evaluation of mortar fluidity and shrinkage reduction performance>
The mortar fluidity and shrinkage reduction performance were evaluated by combining the above polymers 1 to 10 or the comparative polymers 1 to 6 with the above polycarboxylic acid-based water reducing agent PC-1 to 2 by the following method. The amount of each compound added 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)
Ordinary Portland cement containing mortar shown below (JIS R 5210 compliant product) 500 g
Water (deionized water) + additive 225g
Land sand from Oi River (removes sand with a particle size of 5 mm or more; density 2.69 g / cm ³ ) 1350 g
Therefore, according to the method of JIS R5201-1997 Annex 2, the kneading of the mortar composition in the above-mentioned measurement of the values of the conditions (1) and (2) in the present invention was carried out. After the kneading is completed, the mortar is taken out from the kneading pot, and a steel slump cone (upper end inner diameter 50 ± 0.5 mm, lower end inner diameter 100 ± 0.5 mm, height 150 ± 0.5 mm) described in JIS A1171 is used. Specimens for measuring mortar fluidity and evaluating shrinkage reduction performance were prepared according to the methods shown below.
<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 to the top of the slump cone and poke it 15 times with a stick. In addition, after smoothing the top surface of the mortar to the top surface of the slump cone, immediately gently pull the slump cone vertically. Next, after confirming that the spread of the mortar had stopped, the major axis of the expanded mortar and the diameter orthogonal to the major axis were measured, respectively, and the average value was taken as the mortar fluidity.
<Evaluation of shrinkage reduction performance>
(Creation of specimen)
The specimen (4 × 4 × 16 cm) used for the evaluation of shrinkage reduction performance was carried out according to the method of JIS R 5201 Annex 2 using the mortar kneaded according to the above-mentioned <Kneading of mortar composition>.
Silicone grease was applied to the mold in advance so that it could be easily removed, and gauge plugs were attached to both ends. Immediately after kneading, the mortar was placed in a mold, sealed and stored at 20 ° C. for initial curing (sealing curing). After 1 day, the mold was removed, and the silicon grease adhering to the specimen was washed with water using a scrubbing brush, and then cured in still water at 20 ° C. for 6 days (underwater curing).
(Measurement of length change)
A dial gauge (manufactured by Nishinihon Testing Machine Co., Ltd.) was used in accordance with 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. Then, it was stored in a constant temperature and humidity chamber set at a temperature of 20 ± 1 ° C. and a humidity of 60 ± 5%, and the length was measured in a timely manner.
At this time, the shrinkage reduction rate represented by the following formula was calculated, and the shrinkage was set to a value capable of reducing the shrinkage when the composition of the present invention was added with respect to the shrinkage amount of the reference mortar not using the composition of the present invention. The larger the value, the more the shrinkage could be reduced.

When the polymers 1 to 10 are used in Examples 1 to 12, the combination of PC-1 and 2 is equivalent to the amount of the water reducing agent added in a smaller amount as compared with Comparative Examples 1 and 11 in which these polymers are not used. Mortar fluidity was shown. On the other hand, in Comparative Examples 6 to 10 and 15 in which the polymers 1, 3, 4, 6, 8 and 9 were used alone, the mortar fluidity values were lower than those of the others. It was clarified that the effect of improving the mortar fluidity was hardly observed. By combining such a polymer that does not contribute to the improvement of mortar fluidity by itself 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.
Further, by using the above polymers 1 to 10 as the shrinkage reducing agent, it is possible to exhibit the same or higher shrinkage reducing property with a smaller amount of addition than when PEG1000, PEG4500 and SP-200 are used as the shrinkage reducing agent. It became clear.

Claims (2)

An admixture material composition containing a shrinkage reducing agent for hydraulic materials and a polycarboxylic acid-based water reducing agent.
The water-hardening material for shrinkage reducing agents, see contains at least one compound selected from the group consisting of: (I) ~ (V),
The content ratios of the shrinkage reducing agent for hydraulic materials and the polycarboxylic acid-based water reducing agent are 30 to 90% by mass and 10 to 70% by mass, respectively, with respect to 100% by mass of the admixture material composition. Material composition.
(I):
The following formula (1);

(In the formula (1), R ^{1 to} R ³ represent the same or different hydrogen atom or methyl group. R ⁴ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. P represents a number from 0 to 5, q is a number of 0 or 1, and n is an average addition molar of an oxyalkylene group. The structural unit (I) represented by (a number of 7 to 300) representing a number and the following formula (2);

(In formula (2), R ^{6 to} R ⁸ represent the same or different hydrogen atom, methyl group or − (CH ₂ ) _m COOZ'group, where m is an integer of 0 to 2. , Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). A polymer having II) and
In the polymer, the ratio of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of the total structural unit, and the ratio of the structural unit (II) is 100 mol% with respect to the total structural unit. , 10-59 mol% and a weight average molecular weight of 4000-32000: Polymer (II):
The following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In the 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. Represents 18 oxyalkylene groups. 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, 0 to 2000, and f + g = 1 to 2000. Y represents the residue of the compound having active hydrogen. K and l are the same or different, 0 to 6. However, k + l is 1 or more.) A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer.
The ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer and contains
In the polymer, the proportion of structural units derived from unsaturated carboxylic acid-based monomers is 0.1 to 12% by mass with respect to 100% by mass of all structural units, and the weight average molecular weight of the polyether compound is , 1500-50000 Polymer (III):
A copolymer having a structure in which a polymer chain (A) derived from an ethylenically unsaturated monomer component and a terminal of a (poly) alkylene glycol chain (B) are bonded via a binding site (X).
The ethylenically unsaturated monomer contains an unsaturated anionic monomer and contains
In the copolymer, the ratio 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, and the (poly) alkylene glycol chain is formed (poly). ) (Poly) alkylene glycol-based block copolymer (IV): alkylene glycol having a weight average molecular weight of 1500 to 50,000.
A polyalkylene glycol compound in which at least two ends of a linear or branched polyalkylene glycol chain are bonded to an organic residue exhibiting an adsorptive ability to at least one of a metal, a metal compound and a metal ion.
The polyalkylene glycol compound has a weight average molecular weight of 1500 to 50,000 of the polyalkylene glycol forming the polyalkylene glycol chain.
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 phosphite 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-based monomer, and the ratio of the structural unit derived from the unsaturated carboxylic acid-based monomer is the total structure. A polyamine compound having an acid group-containing side chain which is 25 to 99 mol% with respect to 100 mol% of a unit. A hydraulic material composition containing a shrinkage reducing agent for a hydraulic material, a polycarboxylic acid-based water reducing agent, and a hydraulic material.
The water-hardening material for shrinkage reducing agent is viewed contains at least one compound selected from the group consisting of: (I) ~ (V),
The ratios of the shrinkage reducing agent for hydraulic material and the polycarboxylic acid-based water reducing agent to the hydraulic material in terms of solid content were 0.0001 to 10% by mass and 0.001 to 10% by mass, respectively. A hydraulic material composition having a compounding ratio (mass of shrinkage reducing agent) / (mass of water reducing agent) with a polycarboxylic acid-based water reducing agent of 97/3 to 70/30.
(I):
The following formula (1);

(In the formula (1), R ^{1 to} R ³ represent the same or different hydrogen atom or methyl group. R ⁴ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. P represents a number from 0 to 5, q is a number of 0 or 1, and n is an average addition molar of an oxyalkylene group. The structural unit (I) represented by (a number of 7 to 300) representing a number and the following formula (2);

(In formula (2), R ^{6 to} R ⁸ represent the same or different hydrogen atom, methyl group or − (CH ₂ ) _m COOZ'group, where m is an integer of 0 to 2. , Z'represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group. Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). A polymer having II) and
In the polymer, the ratio of the structural unit (I) is 70 to 97% by mass with respect to 100% by mass of the total structural unit, and the ratio of the structural unit (II) is 100 mol% with respect to the total structural unit. , 10-59 mol% and a weight average molecular weight of 4000-32000: Polymer (II):
The following formula (3);
_{^{[V- (OA 1) f -}} ] k Y [- (B 1 O) g -W] l (3)
(In the 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. Represents 18 oxyalkylene groups. 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, 0 to 2000, and f + g = 1 to 2000. Y represents the residue of the compound having active hydrogen. K and l are the same or different, 0 to 6. However, k + l is 1 or more.) A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer.
The ethylenically unsaturated monomer contains an unsaturated carboxylic acid-based monomer and contains
In the polymer, the proportion of structural units derived from unsaturated carboxylic acid-based monomers is 0.1 to 12% by mass with respect to 100% by mass of all structural units, and the weight average molecular weight of the polyether compound is , 1500-50000 Polymer (III):
A copolymer having a structure in which a polymer chain (A) derived from an ethylenically unsaturated monomer component and a terminal of a (poly) alkylene glycol chain (B) are bonded via a binding site (X).
The ethylenically unsaturated monomer contains an unsaturated anionic monomer and contains
In the copolymer, the ratio 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, and the (poly) alkylene glycol chain is formed (poly). ) (Poly) alkylene glycol-based block copolymer (IV): alkylene glycol having a weight average molecular weight of 1500 to 50,000.
A polyalkylene glycol compound in which at least two ends of a linear or branched polyalkylene glycol chain are bonded to an organic residue exhibiting an adsorptive ability to at least one of a metal, a metal compound and a metal ion.
The polyalkylene glycol compound has a weight average molecular weight of 1500 to 50,000 of the polyalkylene glycol forming the polyalkylene glycol chain.
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 phosphite 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-based monomer, and the ratio of the structural unit derived from the unsaturated carboxylic acid-based monomer is the total structure. A polyamine compound having an acid group-containing side chain which is 25 to 99 mol% with respect to 100 mol% of a unit.