JP6843497B2 - Hydraulic material composition - Google Patents

Description

The present invention relates to hydraulic material compositions. More specifically, the present invention relates to a hydraulic material composition suitable as a cement composition such as cement paste, mortar, and concrete.

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. In such a hydraulic material, after curing, unreacted moisture remaining inside is dissipated due to outside air temperature, humidity conditions, etc., and drying shrinkage, which is considered to be caused by this, progresses, causing cracks in the cured product. There is a problem that the strength and durability are lowered. When the strength and durability of civil engineering and building structures are reduced, serious problems such as a decrease in safety and an increase in repair costs will occur.

With respect to such problems, the importance of a shrinkage reducing agent for hydraulic materials that suppresses the progress of drying shrinkage in a cured product of hydraulic materials has been recognized, and technological innovations have been actively carried out.
As a conventional shrinkage reducing agent, a polymer having a structural unit derived from an unsaturated carboxylic acid-based monomer and a structural unit derived from an ethylenically unsaturated monomer having an oxyalkylene group in a side chain (Patent Documents 1 to 3). A graft polymer obtained by graft-polymerizing an ethylenically unsaturated monomer to a polyether compound having a structure in which one oxyalkylene chain is bonded to a residue of a compound having one active hydrogen (see Patent Document 4). 5, 5) and the like are disclosed.

Special Table 2007-528397 Japanese Unexamined Patent Publication No. 2007-297241 JP-A-2007-76972 Patent No. 4437369 JP-A-2002-293596

As described above, polymers having various structures have been proposed as shrinkage reducing agents, but none of them is sufficient in terms of shrinkage reduction performance, and we will develop shrinkage reduction agents that exhibit even higher shrinkage reduction performance. There was room for ingenuity. In addition, the use of shrinkage reducing agents may reduce the freeze-thaw resistance of hydraulic materials. In order for the cured product of the hydraulic composition to have sufficient strength, it is also important that the freeze-thaw resistance is good, and a hydraulic material composition having both shrinkage reduction performance and freeze-thaw resistance is required. Has been done.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a hydraulic material composition having both shrinkage reduction performance and freeze-thaw resistance.

The present inventor has studied various hydraulic material compositions that have both shrinkage reduction performance and freeze-thaw resistance. As a result, the hydraulic material composition is defined to contain a hydraulic material, a shrinkage reducing agent, and an air entraining agent, and shrinkage. As the reducing agent, the mortar composition to which the shrinkage reducing agent is added uses a shrinkage reducing agent that satisfies a predetermined condition for the flow value, and the ratio of the air entraining agent to the hydraulic material in the composition and the shrinkage reducing agent. It was found that the hydraulic material composition is excellent in shrinkage reduction performance and freeze-thaw resistance when the mass ratio with the air entraining agent is within a predetermined range, and the above-mentioned problems can be solved brilliantly. We came up with the idea of being able to do this, and arrived at the present invention.

That is, the present invention is a hydraulic material composition containing a hydraulic material, a shrinkage reducing agent and an air entraining agent, and the shrinkage reducing agent contains a compound satisfying the following conditions (1) to (3). The content of the air entraining agent is 0.002 parts by weight or more with respect to 100 parts by weight of the hydraulic material, and the mass ratio of the shrinkage reducing agent and the air entraining agent is 99.98 / 0.02 to 80/20. It is a hydraulic material composition characterized by being present.
(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 compound. Ratio of values: (15 stroke flow value of the compound-containing mortar composition) / (15 stroke flow value of the mortar not containing the compound) × 100 is 120 or less (2) JASS 5 M402 compliant mortar not containing the compound The ratio of the 15-stroke flow value 2 hours after the start of kneading and the 15-stroke flow 10 minutes 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%. Ratio to value ratio: (ratio of 15 stroke flow values after 2 hours) / (ratio of 15 stroke flow values after 10 minutes) x 100 is 110 or less (3) Monomer component which is a raw material of the compound The ratio of the compound having an acid group in 100 mol% is 1 to 99 mol%.
The present invention will be described in detail below.
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.

The hydraulic material composition of the present invention contains a hydraulic material, a shrinkage reducing agent satisfying the above conditions (1) and (2), and an air entraining agent (AE agent). The conditions (1) and (2) above mean that the effect of the shrinkage reducing agent on improving the flow value and the flow retention of the mortar composition is not too high.
In the present invention, a hydraulic material composition containing a shrinkage reducing agent having such a predetermined dispersion performance and an air entraining agent in a predetermined ratio in addition to the hydraulic material has the shrinkage reduction performance and freeze-thaw resistance. We have found that both are excellent. The JASS 5 M402 compliant mortar is described in Examples described later.
The hydraulic material composition of the present invention may contain one kind each of a shrinkage reducing agent and an air entraining agent, or may contain two or more kinds.

When the ratio of the 15-stroke flow value of the compound-containing mortar composition of (1) to the 15-stroke flow value of the mortar not containing the compound is 120 or less, the compound has a high performance of improving the flow value. However, the ratio is preferably 118 or less. More preferably, it is 115 or less. The ratio is preferably 90 or more, more preferably 95 or more, and even more preferably 97 or more.

The ratio of the flow value of 15 strokes 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 is not too high in performance for improving flow retention, but the ratio is preferably 109 or less. More preferably, it is 105 or less. The ratio is preferably 85 or more, more preferably 90 or more, and even more preferably 95 or more.
The flow value in the above (1) and (2) can be measured by the method described in the examples.

In the compound (polymer) contained in the shrinkage reducing agent of the present invention, the proportion of the monomer having an acid group in 100 mol% of the monomer component which is the raw material of the compound is 1 to 99 mol%.
Since the flow values of the above (1) and (2) are affected by the amount of acid of the compound, the flow values of the above (1) and (2) can be adjusted by setting the amount of acid of the compound within a predetermined range. It will be easier to meet the requirements of. The proportion of the monomer having an acid group in 100 mol% of the monomer component which is the raw material of the compound is preferably 10 to 97 mol%, more preferably 15 to 97 mol%, and particularly. It is preferably 20 to 97 mol%, and most preferably 25 to 95 mol%.
When the compound is a polymer, the content ratio of the acid group-containing monomer in the monomer component may be in the above range, and the compound satisfying the flow values of (1) and (2) above. Will be easier to obtain.

The hydraulic material composition of the present invention contains 0.002 parts by weight or more of an air entraining agent with respect to 100 parts by weight of the hydraulic material. By containing the air entraining agent in such a ratio, the decrease in freeze-thaw resistance due to the inclusion of the shrinkage reducing agent is suppressed, and the hydraulic material composition is excellent in both shrinkage reduction performance and freeze-thaw resistance. Can be. The content of the air entraining agent is preferably 0.0025 parts by weight or more, 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 department. Further, in order to make the freeze-thaw resistance particularly good, the content of the air entraining agent is preferably 0.1 part 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.
Further, in the hydraulic material composition of the present invention, the mass ratio of the shrinkage reducing agent and the air entraining agent is 99.98 / 0.02 to 80/20, and the mass ratio is preferably 99.96 /. It is 0.04 to 85/15, more preferably 99.9 / 0.1 to 90/10, and particularly preferably 99.8 / 0.2 to 90/10.
In order to make the hydraulic material composition particularly excellent in both shrinkage reduction performance and freeze-thaw resistance, the mixing ratio of the air entraining agent and the mass ratio of the shrinkage reducing agent and the air entraining agent should be in such a range. Is preferable. The present invention has found the type of shrinkage reducing agent for obtaining a hydraulic material composition having excellent shrinkage reduction performance and freeze-thaw resistance, and the optimum blending ratio of an air entraining agent used in combination therewith. It can be said.

By containing the shrinkage reducing agent, the hydraulic material composition of the present invention has an effect of reducing the shrinkage that occurs when the hydraulic material dries, and reduces or prevents cracks in the cured product and has a filling property. It is effective in improving, preventing warping, and preventing peeling.
The content of the shrinkage reducing agent 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. 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, further preferably 0.005 to 3% by weight, and most preferably 0.01 to 1% by weight.

The compound contained in the shrinkage reducing agent is preferably a polymer, and the weight average molecular weight is preferably 2000 to 35000. It is more preferably 2000 to 30000, and even more preferably 3000 to 25000.
The weight average molecular weight of the compound can be measured by gel permeation chromatography (GPC) under the conditions described in Examples described later.

The compound contained in the shrinkage reducing agent of the present invention preferably has a surface tension of 55 to 70 mN / m in a 5% by mass aqueous solution of the compound. When the compound has such a surface tension, it becomes easy to adjust the amount of air in the hydraulic material composition, and further, it does not affect the action of the defoaming agent and the air entraining agent (AE agent), and as a result, It is possible to suppress a decrease in freeze-thaw resistance, which has been a problem with conventional shrinkage reducing agents. The surface tension of the 5% by mass aqueous solution of the compound is more preferably 57 to 70 mN / m, further preferably 60 to 70 mN / m, and particularly preferably 60 to 65 mN / m.
The surface tension of the 5% by mass aqueous solution of the compound can be measured by any of the following procedures.
<Surface tension measurement condition (1)>
Measuring equipment: Dynamometer (trade name) manufactured by BYK-Chemie
Ring: Platinum φ19.5mm
Standard solution: pure water 72.8 mN / m (20 ° C)
Table speed: 1.5 mm / min Measurement temperature: 20 ° C
<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 the compound for which the surface tension is measured 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) Next, attach a thoroughly washed platinum ring to a dynometer, submerge it in a standard solution (pure water) whose temperature has been adjusted to 20 ° C. by 3 mm, and place a table on which this standard solution is placed at 1.5 mm / Lower at a rate of minutes. At this time, the point where the value indicated by the dynometer becomes maximum is calibrated as the surface tension of water. Next, a fully washed platinum ring is submerged in a sample solution adjusted to 20 ° C. by submerging 3 mm, and the table on which this aqueous solution is placed is lowered at a speed of 1.5 mm / min, and the value indicated by the dynometer becomes the largest. Let the point be the surface tension of the compound.
<Surface tension measurement condition (2)>
Measuring equipment: Dynamic surface tension meter (SITAScience line t60 (manufactured by MESSTECHNIK))
<Measurement procedure>
(1) An aqueous solution of a shrinkage reducing agent sample is prepared by the method described in the measurement procedure (1) and (2) of the surface tension measurement condition (1).
(2) Measuring surface tension A 2% by mass aqueous solution of a compound having a solid content is prepared, the temperature is adjusted to 20 ° C., and then the surface tension is measured using a dynamic surface tension meter (SITAScience line t60 (manufactured by MESSTECHNIK)). Is carried out, and the value measured at Frequency 0.5 Hz is used as the surface tension of the corresponding compound.

The content of the compound satisfying the above conditions (1) to (3) in the shrinkage reducing agent is not particularly limited as long as the effects of the present invention are exhibited, but is 60% by weight or more of the total shrinkage reducing agent. It is preferably 70% by weight or more, more preferably 80% by weight or more, and most preferably 90% by weight or more.

The compound contained in the shrinkage reducing agent is not particularly limited as long as it satisfies the conditions (1) to (3) above, but is composed of a polymer chain derived from an ethylenically unsaturated monomer, a polyalkylene glycol chain and a polyamine chain. It is preferable that the polymer has at least one polymer chain selected from the above group in the structure. As long as it is a polymer having these structural characteristics, it is easy to obtain a polymer satisfying the above conditions (1) and (2), so that it is possible to design polymers having various structures.

When the compound contained in the shrinkage reducing agent is the polymer, it is preferably at least one compound selected from the group consisting of the following (I) to (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. It represents a number and is a number from 1 to 300.) And the structural unit represented by 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, an organic amine group or a hydrocarbon group). Polymer (II) with structural units:
The following formula (3);
W- (R ⁹ O) _r- Y (3)
(In the formula (3), R ⁹ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. R represents the average number of moles of the oxyalkylene group added, and is a number of 1 to 2000. W and Y are the same or different and represent a hydrogen atom or a methyl group.) Polymer (III): A polymer obtained by graft-polymerizing an ethylenically unsaturated monomer to a polyether compound represented by.
A (poly) alkylene glycol-based block 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). Block Polymer (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 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 (V):
Polyamine compound having an acid group-containing side chain

In the following, details of each of the compounds (I) to (V) will be described.
<First preferred form>
The compound contained in the shrinkage reducing agent in the present invention is 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 (1 to 300), which represents 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, an organic amine group or a hydrocarbon group). The polymer having the structural unit (II) is the first preferred form of the compound contained in the shrinkage reducing agent in the present invention.
The compound having the first preferred form may contain one structural unit (I) represented by the above formula (1) and one structural unit (II) represented by the formula (2), respectively. The above may be included.

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 group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group and a 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, q represents a number of 0 or 1, and a preferable combination of p and q is a combination of p of 1 or 2 and q of 0, or It is a combination of 0 in p and 1 in q.

In the above formula (1), n represents the average number of moles of oxyalkylene group added, and is a number of 1 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 1 to 150. It is more preferably 1 to 100, still more preferably 1 to 80, particularly preferably 1 to 50, and most preferably 1 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, an ester 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 transesterifying 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. Or, it is a case where ^{any one of R 6 to} R ⁸ is in the form of an anhydride with the − (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, triethylamine group and the like can be mentioned.
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. As the hydrocarbon group having 1 to 30 carbon atoms, 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-xysilyl, 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.

In the above formula (2), when Z is a hydrocarbon group, it is preferably a hydrocarbon group having 1 to 30 carbon atoms. When Z is a hydrocarbon group and the number of carbon atoms in Z is 31 or more, it becomes difficult to balance the hydrophilicity and hydrophobicity of the polymer, the air entrainment becomes high, and it becomes difficult to adjust the amount of air. There is a risk of reduced strength and reduced freeze-thaw resistance. The number of carbon atoms in Z is preferably 1 to 18, more preferably 1 to 12, still more preferably 1 to 8, and most preferably 1 to 3.
Examples of such a hydrocarbon group having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl and nonyl. , Decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl and 2-ethylhexyl, tetradecyl, octadecyl, icosyl and other linear and branched alkyl groups; cyclopentyl, cyclohexyl , Cycloheptyl, cyclooctyl and other cyclic alkyl groups; phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, Examples thereof include aryl groups such as benzhydryl, trityl and pyrenyl.
Of these, alkyl groups having 1 to 3 carbon atoms of methyl, ethyl, propyl, and isopropyl are preferable in consideration of dispersibility of the hardened cement product and reduction of drying shrinkage.

^{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. Further, it is also a preferable form that all of ^{R 6 to} R ^{8 are hydrogen atoms or methyl groups.}

Examples of the monomer forming the structural unit (II) represented by the above formula (2) include unsaturated carboxylic acid-based monomers. As the unsaturated carboxylic acid-based monomer, an unsaturated monocarboxylic acid-based monomer, an unsaturated dicarboxylic acid-based monomer, or the like is preferable, and as the unsaturated monocarboxylic acid-based monomer, the unsaturated monocarboxylic acid-based monomer is contained in the molecule. It may be a monomer having one unsaturated group and one group capable of forming a carboanion, and may be, for example, (meth) acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2. -Pentenoic acid, itaconic acid, etc .; these monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like 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, and methoxyethyl (meth). Hydroxyl or alkoxy group-containing (meth) acrylate compounds such as meta) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl ethyl (meth) acrylate, and methoxypropyl (meth) acrylate; unsaturated monocarboxylic acid-based simple compounds as described above. Amides of metric and amines with 1 to 30 carbon atoms, (meth) acrylamide, methyl (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) Unsaturated amides such as acrylamide; diesters of the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or (poly) alkylene glycols having 2 to 500 additional moles of these glycols; maleamic acid and carbon atoms. Half-amides with 2 to 18 glycols or (poly) alkylene glycols with an additional molar number of 2 to 500 of these glycols; hexanediol di (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylpropandi ( Polyfunctional (meth) acrylates such as meta) acrylates; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxipropyl 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. Amin salts; vinyl aromatics such as styrene, α-methylstyrene, bromostyrene, chlorostyrene, vinyltoluene, p-methylstyrene; α-olefins such as hexene, heptene, decene; methylvinyl ether, ethylvinyl ether, butylvinyl ether Etc. Al Kill vinyl ethers; Allyl esters such as allyl acetate; Allyls such as allyl alcohol.

Alcandiol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate; butadiene, isoprene, Dienes such as isobutylene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile; vinyl acetate, vinyl propionate and the like. Unsaturated esters; (meth) aminoethyl acrylate, (meth) methylaminoethyl acrylate, (meth) dimethylaminoethyl acrylate, (meth) dimethylaminopropyl acrylate, (meth) dibutylaminoethyl acrylate, vinyl Unsaturated amines such as pyridine; Divinyl aromatics such as divinylbenzene; Cyanurates such as triallyl cyanurate; Polydimethylsiloxane propylaminomale amidoic acid, polydimethylsiloxane aminopropylene aminomale amidoic acid, polydimethylsiloxane-bis -(Propylaminomale amidoic acid), polydimethylsiloxane-bis- (dipropyleneaminomale amidoic 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 compound of the first preferred form, the mass ratio of the structural unit (I) represented by the above formula (1), the structural unit (II) represented by the formula (2), and the other structural unit (III). Is preferably structural unit (I) / structural unit (II) / structural unit (III) = 99.5 to 50 / 0.5 to 50/0 to 49.5. More preferably, it is 98 to 65/2 to 35/0 to 33, further preferably 98 to 75/2 to 25/0 to 23, and particularly preferably 98 to 85/2 to 15/0. It is 13, and most preferably 97 to 90/3 to 10/0 to 7.

In the compound of the first preferred form, the molar ratio of the structural unit (I) represented by the above formula (1), the structural unit (II) represented by the formula (2), and the other structural unit (III). Is preferably structural unit (I) / structural unit (II) / structural unit (III) = 99 to 1/1 to 99/0 to 98. More preferably, it is 75 to 3/25 to 97/0 to 72, further preferably 75 to 10/25 to 90/0 to 65, and even more preferably 70 to 30/30 to 70/0. It is ~ 40, more preferably 70-40 / 30-60 / 0-30, and most preferably 65-50 / 35-50 / 0-15.

The method for producing the compound (polymer) having the first preferred form is not particularly limited, but it is preferable to polymerize the monomer component as a raw material of the polymer 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 thereof 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 preferred form>
The compound contained in the shrinkage reducing agent in the present invention is the following formula (3);
W- (R ⁹ O) _r- Y (3)
(In the formula (3), R ⁹ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. R represents the average number of moles of the oxyalkylene group added, and is a number of 1 to 2000. It is the present invention that W and Y are polymers obtained by graft-polymerizing an ethylenically unsaturated monomer to a polyether compound represented by the same or different hydrogen atom or methyl group. It is the second preferred form of the compound contained in the shrinkage reducing agent in.

The graft polymer 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. Including. This makes it possible to prevent sudden thickening due to runaway of the polymerization reaction in the above-mentioned graft polymerization. The content of the unsaturated carboxylic acid-based monomer in the ethylenically unsaturated monomer is not particularly limited as long as it exerts the effects of the present invention, but is 50 of the entire ethylenically unsaturated monomer. It is preferably mass% or more. More preferably, it is 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass, that is, an ethylenically unsaturated monomer. Are all unsaturated carboxylic acid-based monomers.

As the α, β-unsaturated dicarboxylic acid and / or its anhydride, the same one as the unsaturated dicarboxylic acid-based monomer in the first preferred form 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 preferred 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, further 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, dotecilmaleimide, 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) achlorine; 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, vinylpyrrolidone, 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 graft polymer of the second preferred form is prepared by adding the ethylenically unsaturated monomer to the polyether compound. A graft polymer obtained by graft-polymerizing the unsaturated carboxylic acid-based monomer in the ethylenically unsaturated monomer at a usage amount of 0.1 to 50% by weight based on the polyether compound. Is preferable. 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. The curing retardability of the hard material may increase, or the viscosity of the reaction mixture when preparing the hydrophilic graft polymer may increase, making it difficult to handle. It is more preferably 0.5 to 30% by weight, further preferably 1 to 20% by weight, and particularly preferably 2 to 10% by weight.

In the graft polymer of the second preferred form, the monomer component that is the raw material of the compound is a polyether compound that is a raw material of the graft polymer, an unsaturated carboxylic acid-based monomer, and an unsaturated carboxylic acid. It is an ethylenically unsaturated monomer other than an acid-based monomer, and is an ethylenically unsaturated monomer other than a polyether compound and an unsaturated carboxylic acid-based monomer as raw materials, and an unsaturated carboxylic acid-based monomer. The molar ratio with the monomer is preferably 99 to 1/1 to 99/0 to 98. More preferably, it is 97 to 3/3 to 97/0 to 94, further preferably 75 to 5/25 to 95/0 to 70, and even more preferably 65 to 5/35 to 95/0. It is 0 to 60, particularly preferably 50 to 5/50 to 95/0 to 45, and most preferably 50 to 8/60 to 92/0 to 32.

The polyether compound in the graft polymer of the second preferred form is used as a raw material for preparing the 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 preferred form, it is important to appropriately balance the hydrophilicity and the hydrophobicity of the polyether compound. As an index showing such a balance between hydrophilicity and hydrophobicity, for example, there is HLB. To quantify the HLB, for example, use the Griffin formula described in "Surfactant-Physical Properties / Applications / Chemical Ecology-" (8th print, August 10, 1991, published by Kodansha). It can be calculated according to the above. 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 graft polymer of the second preferred form, the polyether compound is a compound represented by the above 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), 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 general formula (1) has a function of imparting appropriate hydrophobicity to the graft polymer.
The r in the above formula (3) 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, more preferably 500 or less.

^{In the group represented by − (R 9} O) − in the above formula (3), the oxyalkylene group having 2 to 18 carbon atoms may be one kind or two or more kinds. 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 group represented by − (R 9} O) − in the above formula (3), the ratio of the average number of moles of oxyethylene groups to the average number of moles of oxyalkylene groups having 2 to 18 carbon atoms is 50. % Or more is preferable. More preferably, it is 60% or more, further preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more.

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. These may be used alone or in combination of two or more.

In the graft polymer of the second preferred form, as the polyether compound, a derivative of the compound represented by the above formula (3) may be contained together with the compound represented by the above formula (3), and the above formula (3) may be contained. ) May contain a derivative of the compound represented by the above formula (3). 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 product obtained by reacting a 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 can be mentioned.

The weight average molecular weight (Mw) of the compound represented by the above formula (3) is not particularly limited, and is preferably 1000 to 1000000, for example. It is more preferably 2000 to 50000, still more preferably 2000 to 40,000, and particularly preferably 3000 to 35000. 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.

In the graft polymerization for preparing the graft polymer of the second preferred form, the ethylenically unsaturated monomer is added starting from the graft site generated when a hydrogen atom or a halogen atom is extracted from the polyether compound. It is done by polymerization.

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. 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 method of graft polymerization is not particularly limited as long as it is a method capable of graft-polymerizing 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. Alkali metal and alkaline earth metal carbonates; 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 preferred form>
In the compound contained in the shrinkage reducing agent in the present invention, the polymer chain (A) derived from the ethylenically unsaturated monomer component and the end of the (poly) alkylene glycol chain (B) are bonded via a bond site (X). The (poly) alkylene glycol-based block copolymer having the above-mentioned structure is a third preferred form of the compound contained in the shrinkage reducing agent in the present invention.

The third preferred form of the (poly) alkylene glycol-based block copolymer is a polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer and a (poly) alkylene glycol-based block copolymer. It is characterized in that it has a structure in which the end of the polymer chain (B) according to the structural unit is bonded via a binding site (X), whereby an excellent shrinkage reducing effect can be exhibited.
As long as the (poly) alkylene glycol-based block copolymer of the third preferred form has such structural characteristics, the structure of the copolymer as a whole is not particularly limited, but the following (1) to (1) to ( It is preferably a copolymer having any of the structures of 4).
(1) The end of the polymer chain (A) derived from a vinyl-based monomer component in which only one end of the linear polymer chain (B) contains an unsaturated anion-based monomer, and the binding site (X). A copolymer having a structure bonded via.
(2) Both ends of the linear polymer chain (B) have a binding site (X) with the end of the polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer. A copolymer having a structure bonded via a polymer.
(3) The bonding site (X) between the polymer chain (A) derived from the vinyl-based monomer component containing the unsaturated anion-based monomer and the polymer chain (B) by the (poly) alkylene glycol-based structural unit is formed. A multi-branched (poly) alkylene glycol-based block copolymer that requires a mediated bond, and the multi-branched (poly) alkylene glycol-based block copolymer has a polymer chain (B) having a multi-branched structure. A copolymer having a structure in which a part or all of the branched parts are formed, three or more of the branched parts are provided, and the polymer chain (A) is provided at the terminal portion of the partial branched part.
(4) A bonding site (X) between the polymer chain (A) derived from the vinyl-based monomer component containing the unsaturated anion-based monomer and the polymer chain (B) by the (poly) alkylene glycol-based structural unit is formed. A multi-branched (poly) alkylene glycol-based block copolymer that requires a mediated bond, and the multi-branched (poly) alkylene glycol-based block copolymer has a polymer chain (B) having a multi-branched structure. A copolymer having a structure that is a part of a branched portion, has three or more branched portions, and has the polymer chain (A) at the terminal portions of all the branched portions.
In the following, the copolymers having the structures (1) to (4) above are described as (poly) alkylene glycol-based block copolymers (1) to (4), respectively. Next, the specific residues (Z) of the polymer chain (A), the polymer chain (B), the binding site (X), and the residue (Z) of the compound having active hydrogen constituting the branching site of the branched structure will be described. Structure will be described.

[(Poly) alkylene glycol-based block copolymer (1)]
The (poly) alkylene glycol-based block copolymer (1) is a vinyl in which only one end of the polymer chain (B) made of a linear (poly) alkylene glycol-based structural unit contains an unsaturated anionic monomer. It has a structure in which it is bonded to the end of a polymer chain (A) derived from a system monomer component via a binding site (X).
Here, 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 ( When the side chain is bonded to the atom at the end of the main chain of A), it may be bonded to the end of the side chain, but it is preferably the end of the main chain. This point is the same for the copolymers (2) to (4) described later.

The (poly) alkylene glycol-based block copolymer (1) has the following formula (4);
R ^10- (B) _n1- X-A (4)
(In the formula, R ¹⁰ 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. 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 has a structure represented by 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 the (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.

[(Poly) alkylene glycol-based block copolymer (2)]
The (poly) alkylene glycol-based block copolymer (2) is a vinyl-based block copolymer (2) containing an unsaturated anionic monomer at both ends of the polymer chain (B) made of a linear (poly) alkylene glycol-based structural unit. It has a structure in which it is bonded to the end of a polymer chain (A) derived from a monomer component via a binding site (X).
The (poly) alkylene glycol-based block copolymer (2) has the following formula (5);
A-X- (B) _n2- X-A (5)
(In the formula, (B) _n2 represents a polymer chain composed of a (poly) alkylene glycol-based structural unit, B represents the same or different oxyalkylene group having 2 to 18 carbon atoms, and X represents the same or different oxyalkylene group. Differently, it represents an organic residue. A represents a polymer chain derived from a vinyl-based monomer component containing an unsaturated anion-based monomer, which is the same or different. N2 represents an average addition molar of an oxyalkylene group. It represents a number, and is preferably a number having a structure represented by (1 to 1000).
In the above formula (5), the _{polymer chain (B) represented by (B) n2} and the polymer chain (A) represented by A are connected via the binding site (X) represented by X. The point of bonding is the same as in the case of the above-mentioned copolymer (1).

[(Poly) alkylene glycol-based block copolymer (3)]
The (poly) alkylene glycol-based block copolymer (3) is a polymer composed of a polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer and a (poly) alkylene glycol-based structural unit. A multi-branched (poly) alkylene glycol-based block copolymer that requires a bond with the chain (B) via a bonding site (X), and the multi-branched (poly) alkylene glycol-based block copolymer is The polymer chain (B) is a part or all of a branched portion having a multi-branched structure, has three or more branched portions, and has the polymer chain (A) at the terminal portion of a part of the branched portion. It is a multi-branched (poly) alkylene glycol-based block copolymer having a structure having.
The (poly) alkylene glycol-based block copolymer (3) has the following formula (6);

(In the formula, R ¹¹ represents 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. Z1 is an active hydrogen. (B) _n3 represents a polymer chain having the same or different (poly) alkylene glycol-based structural unit, and B represents the same or different carbon number 2 to 2. Represents an oxyalkylene group of 18. X represents the same or different organic residue. A represents a polymer chain derived from a vinyl-based monomer component containing an unsaturated anion-based monomer. N3 represents a polymer chain. , The same or different, represents the average number of moles of oxyalkylene groups added, which is a number of 1 to 1000. M1 and p1 are numbers of 1 or more, and the sum of m1 and p1 is 3 or more). It is preferable that it has the structure represented.
In the above formula (6), the _{polymer chain (B) represented by (B) n3} and the polymer chain (A) represented by A are connected via the binding site (X) represented by X. The point of bonding is the same as in the case of the above-mentioned copolymer (1).

In the above formula (6), m1 represents the number of branch-like portions in which the polymer chain A and the polymer chain (B) _n3 are bonded via the binding site X, and p1 represents the hydrogen atom and the height. Represents the number of branch-like portions to which the molecular chain (B) _{n3 is bound.} The total of m1 and p1 is 3 or more, preferably 10 or less, and more preferably 6 or less. It should be noted that the fact that a part of the end of the polymer chain (B) is bonded to the polymer chain (A) via the binding site (X) means that the entire (poly) alkylene glycol-based block copolymer (3) is bonded. In the copolymer molecule, the percentage of the number of moles of the polymer chain (A) added via the binding site (X) to the number of moles of the terminal sites of all the branched portions of the polymer chain (B). However, it is less than 100 mol%. In the above formula (6), m1 + p1 is the number of moles of the terminal sites of all the branch-like portions of the polymer chain (B), and m1 / m1 + p1 is added to the polymer chain (A) via the binding site (X). It is the ratio of the number of moles. The preferred range of {m1 / (m1 + p1)} × 100 is 10 to 90 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%.
Hereinafter, in the present specification, when the term "branched portion" is simply used, the branched portion in which the polymer chain (A) and the polymer chain (B) are bonded via the binding site X, and 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, and the branched portion in which the polymer chain (B) is bonded. To do. Further, "the polymer chain (B) is a part or all of the branched portion" means that the "branched portion" is a combination of the polymer chain (A) and the polymer chain (B). In the case, the polymer chain (B) becomes a part of the branched portion, and when the “branched portion” is a bond between a hydrogen atom and the polymer chain (B), the polymer chain (B) is branched. Indicates that it will be the entire part.

The (poly) alkylene glycol-based block copolymer (3) in the third preferred form has three or more branched portions.
The preferable lower limit of the number of branch-shaped portions is 5. The preferred upper limit is 20, more preferably 13, and even more preferably 7.
Further, the number of the branch-like portions is preferably equal to the number of active hydrogens in the compound having 3 or more active hydrogens. That is, it is preferable to have a structure in which the branch-like portion is bonded to all of the active hydrogens in the compound having three or more of the active hydrogens. This makes it possible to exhibit even better shrinkage reduction performance.

Here, for example, the structure when the number of the branch-like portions is equal to the number of active hydrogens in the compound having three or more active hydrogens is represented by the following formula (7) or (8). Can be expressed in.

In the above formula (7), the residue of the compound having 3 or more active hydrogens is a glycerin residue (polyhydric alcohol residue, 3 active hydrogens), and the branched portion is bound to all the active hydrogens contained in glycerin. Of the three branched portions, a structure having a polymer chain (A) composed of unsaturated anionic monomer units at the terminal portions of the two branched portions is schematically shown.
Further, in the above formula (8), the residue of the compound having 3 or more active hydrogens is a sorbitol residue (polyhydric alcohol residue, 6 active hydrogens), and the branched portion is bonded to all the active hydrogens contained in sorbitol. However, of the six branched portions, a structure having a polymer chain (A) composed of unsaturated anionic monomer units at the terminal portions of the three branched portions is schematically shown.

[(Poly) alkylene glycol-based block copolymer (4)]
The (poly) alkylene glycol-based block copolymer (4) is a polymer composed of a polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer and a (poly) alkylene glycol-based structural unit. A multi-branched (poly) alkylene glycol-based block copolymer that requires a bond with the chain (B) via a bonding site (X), and the multi-branched (poly) alkylene glycol-based block copolymer is A structure in which the polymer chain (B) is a part of a branched portion of a multi-branched structure, has three or more branched portions, and has the polymer chain (A) at the terminal portions of all the branched portions. This is a multi-branched (poly) alkylene glycol-based block copolymer.
The (poly) alkylene glycol-based block copolymer (4) has the following formula (9);

(In the formula, Z1 represents a residue of a compound having three or more active hydrogens. (B) n4 represents a polymer chain of the same or different (poly) alkylene glycol-based structural unit, and B represents a polymer chain consisting of a (poly) alkylene glycol-based structural unit. Same or different, it represents an oxyalkylene group having 2 to 18 carbon atoms. X represents the same or different organic residue. A represents a polymer chain with an unsaturated anionic monomer unit. N4 Is the same or different, and represents the average number of moles of the oxyalkylene group added, which is a number of 1 to 1000. M2 is preferably a number of 3 or more). ..
In the above formula (9), the _{polymer chain (B) represented by (B) n4} and the polymer chain (A) represented by A are connected via the binding site (X) represented by X. The point of bonding is the same as in the case of the above-mentioned copolymer (1).

In the (poly) alkylene glycol-based block copolymer (4) represented by the above formula (9), in m2, the polymer chain (A) and the polymer chain (B) have a binding site (X). It represents the number of branch-like portions connected via the interposition, and is a number of 3 or more, preferably 10 or less, and more preferably 6 or less.
Further, all the ends of the polymer chain (B) have a bond with the end of the polymer chain (A) derived from the vinyl-based monomer component containing the unsaturated anion-based monomer via the bond site (X). That is, in the total copolymer molecule, the polymer chain (A) is bound to substantially all the terminal parts of the branch-like part, and all the moles of the terminal part of the branch-like part due to the polymer chain (B). It means a copolymer in which the percentage of the number of molecules of the polymer chain (A) is substantially 100 mol% with respect to the number.

The (poly) alkylene glycol-based block copolymer (4) in the third preferred form has three or more branched portions. The preferable value of the number of branched portions is the same as that of the (poly) alkylene glycol-based block copolymer (3).
Here, for example, the structure when the number of the branch-like portions is equal to the number of active hydrogens in the compound having three or more active hydrogens is represented by the following formula (10) or (11). Can be expressed in.

In the above formula (10), the residue of the compound having 3 or more active hydrogens is a glycerin residue (polyhydric alcohol residue, 3 active hydrogens), and (poly) alkylene glycol is added to all the active hydrogens contained in the glycerin. It schematically shows the structure in which the polymer chain (B) of a system constituent unit and the polymer chain (A) of an unsaturated anion-based monomer unit are bonded via a binding site (X).
Further, in the above formula (11), the residue of the compound having 3 or more active hydrogens is a sorbitol residue (polyhydric alcohol residue, 6 active hydrogens), and (poly) alkylene is added to all the active hydrogens contained in sorbitol. It schematically shows a structure in which a polymer chain (B) made of a glycol-based constituent unit and a polymer chain (A) made of an unsaturated anion-based monomer unit are bonded via a binding site (X). ..

Hereinafter, a polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer, a polymer chain (B) composed of a (poly) alkylene glycol-based structural unit, a binding site (X), and active hydrogen. The residue (Z1) of the compound having 3 or more of the above will be described.

[Polymer chain (A) derived from a vinyl-based monomer component containing an unsaturated anion-based monomer]
In the third preferred embodiment, the polymer chain (A) derived from the vinyl-based monomer component containing the unsaturated anion-based monomer contains the vinyl-based monomer component containing the unsaturated anion-based monomer. It is a structural unit having a polymerized structure.
Further, the structural unit having a structure in which the vinyl-based monomer component containing the unsaturated anionic monomer is polymerized can be a structural unit derived from another monomer as long as it has the same structural unit. 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 (12);

(In the formula, at least one of ^{R 12} , R ¹³ , R ¹⁴ , and R ^{15 is −COOM 1} , and R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ 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) is suitable.
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 (12) is opened by the polymerization reaction (double bond (C =). C) corresponds to a single bond (-CC-) structure).

In the above formula (12), the ^{groups represented by M 1} and M ² are a monovalent metal atom and a divalent metal atom, and the organic amine group is a 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 (12) 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 a styrene sulfonic acid or a 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 hydroxyethyl butyl 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.
Examples of the vinyl-based monomer other than the unsaturated anion-based monomer include the compounds listed as specific examples of the compounds forming the other structural unit (III) in the compound of the first embodiment, as well as the compounds. 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; 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 anion-based monomer. Is to become.

In the (poly) alkylene glycol-based block copolymer in the third preferred embodiment, the average number of moles of unsaturated anion-based monomer units introduced in the polymer chain (A) is preferably 1 or more.
Here, when the (poly) alkylene glycol-based block copolymer of the third preferred embodiment has a multi-branched structure, the value of the average number of moles introduced of the unsaturated anion-based monomer unit is It means the average number of moles of unsaturated anionic monomer units contained in one branched portion.
A more preferable lower limit value of the average number of introduced moles is 2, and even more preferably 5. The preferred upper limit is 50, more preferably 30, still more preferably 20, particularly preferably 15, and most preferably 10.
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.
On the other hand, when the average number of moles introduced exceeds 50, the shrinkage reducing agent necessary for obtaining sufficient shrinkage reducing property cannot be added due to the development of dispersibility.

In the (poly) alkylene glycol-based block copolymer in the third preferred embodiment, the unsaturated anion-based monomer in the ethylenically unsaturated monomer component forming the polymer chain (A) and the polyalkylene The mass ratio of the glycol chain (B) is the unsaturated anionic monomer / polyalkylene glycol chain (B) in the ethylenically unsaturated monomer component forming the polymer chain (A) = 0.3 to 70. It is preferably / 99.7 to 30. When the mass ratio of the unsaturated anion-based 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 curing delay property of the water-hard material may increase due to (poly) alkylene glycol-based block copolymerization. is there. It 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 to 60/95. ~ 40.

In the (poly) alkylene glycol-based block copolymer in the third preferred 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. It means a chain (B). That is, an ethylenically unsaturated monomer component (a vinyl-based monomer other than an unsaturated anion-based monomer and an unsaturated anion-based monomer) forming a polymer chain (A), and a polyalkylene glycol chain. (B), the number of moles of the unsaturated anion-based 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 polymer 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, further 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 (poly) alkylene glycol-based structural units 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, alternating 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 also has a (poly) alkylene glycol-based block copolymer weight in the third preferred embodiment when it contains an alkylene oxide having 3 or more carbon atoms. Since it is possible to impart a certain degree of hydrophobicity to the coalescence, when the above-mentioned copolymer is used as a shrinkage reducing agent, it gives a slight structure (network) to the cement particles, and the viscosity of the cement composition is increased. The feeling of stiffness can be reduced. On the other hand, if an alkylene oxide having 3 or more carbon atoms is introduced too much, the hydrophobicity of the copolymer becomes too high, so that the water solubility is lost and the workability is significantly reduced. Since it becomes easy to interact with each other, 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 of the oxyalkylene group 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 preferred embodiment, the average number of repetitions of the alkylene oxide in the polymer chain (B) (the average number of moles of oxyalkylene groups added) is 1 to 1000. Is 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 moles added 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 (the average number of moles of the oxyalkylene group added) means the average number of moles of the alkylene oxide added in one branched portion.

Of the polymer chains (B) contained in the (poly) alkylene glycol-based block copolymer in the third preferred embodiment, the terminal of the polymer chain (B) that is not bonded to the polymer chain (A) via the bond site (X). Is preferably any of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and 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.
It is preferable that ^{R 10} in the above formula (4) ^{and R 11} in the above formula (6) are any of these.

[Binding site (X)]
In the (poly) alkylene glycol-based block copolymer in the third preferred embodiment, the binding site (X) can chemically and stably bond the polymer chain (A) and the polymer chain (B). The structure is not particularly limited as long as it has a structure.
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. Examples include binding sites derived from the structure.
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 a sulfur atom include the following formula (13):

(In the formula, R ¹⁶ 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. 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 16} of the structure represented by the above formula (13) is a site that binds to the polymer chain (B) of the (poly) alkylene glycol-based structural unit, and the sulfur atom (S) contains an unsaturated anion-based 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 ¹⁶ having the structure represented by the above formula (13) is a polymer based on a (poly) alkylene glycol-based structural unit. When bonded to the terminal oxygen atom of the chain (B), the following formula (14):

(In the formula, R ¹⁶ is the same as above.), 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 (15):

(In the formula, R ¹⁷ is a mercaptocarboxylic acid residue, for example, a linear or branched alkylene group having 1 to 18 carbon atoms, a phenyl group, an alkylphenyl group, a pyridinyl group, thiophene, pyrrole, furan, thiazole and the like. 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) made of the (poly) alkylene glycol-based structural unit and the following formula (16):

(In the formula, R ¹⁷ is the same as above.) It will form the site indicated by, and will contain an ester bond at this site.

(Ii) Binding 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 (17). Structures derived from the azo initiator are preferred.

(In the formula, R ¹⁸ is independent of each other and is partially substituted with an alkylene group having 1 to 20 carbon atoms (the alkylene group is partially substituted with an alkyl group, an alkenyl group, a hydroxyl group, a cyano group, a carboxyl group, an amino group 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 ¹⁹ 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 ²⁰ 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 the above can be mentioned.
More preferably, an azo initiator represented by the following formula (18) can be mentioned.

The azo initiator represented by the above formula (18) 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 (17) and (18) is the structure represented by the following formulas (19) and (20).

^(Wherein, R ^18, R ^{19, R 20} are the same as ^{R 18,} R ^{19, R 20} in the formula (17))

This is the side where the carbon of the carbonyl group in the formula (20) is bonded to the polymer chain (B) of the (poly) alkylene glycol-based structural unit.

(Iii) Binding site Derived from Residue Containing Phosphorus Atom As a binding site containing a phosphorus atom, for example, the following formula (21):

(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 hypophosphate (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 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 hypophosphate is preferably a salt formed by hypophosphorous acid and either a metal, ammonia or an organic amine. As the metal, an alkali metal, an 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. A compound converted to a −SH group; (poly) by reacting diethyl (DEAD) azodicarboxylate with triphenylphosphine in the presence of (poly) alkylene glycol and thioacetic acid, and then performing alkaline hydrolysis. A compound in which the -OH group at the end of an alkylene glycol is converted to a -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 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 sulfur atom content is within the above range, the (poly) alkylene glycol-based block copolymer in the third preferred form can be more efficiently produced by the production method described later.

As a preferable form of the (poly) alkylene glycol-based block copolymer in the third preferred form, the polymer chain (A) and the polymer after 15 minutes in a 2% by mass alkaline aqueous solution of the copolymer are also used. The decomposition rate into the chain (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) Calculate the hydrolysis rate from the GPC chart before and after the reaction.

When the (poly) alkylene glycol-based block copolymer in the third preferred embodiment is the above-mentioned (poly) alkylene glycol-based block copolymers (1) and (2), the particularly preferable structure is The structures are represented by the following equations (22) and (23), respectively. When the (poly) alkylene glycol-based block copolymer in the present invention is the above-mentioned (poly) alkylene glycol-based block copolymers (3) and (4), particularly preferable structures among them are the following formulas, respectively. It is a structure shown in (24) and (25).

In formulas (22) to (25), R ²¹ 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. R ²² represents the same or different hydrogen atom or methyl group. Z1 represents the residue of a compound having 3 or more active hydrogens. N5 and r1 represent the average number of moles of oxyethylene group added. It represents 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), and q1 is a number of 1 to 50 (preferably a number of 1 to 50). 1 to 30). M4 and p2 are numbers of 0 or more, respectively, and the total of m4 and p2 is 3 or more. M5 is a number of 3 or more.)
In the structures of the above formulas (22) to (25), the unsaturated carboxylic acid-based monomer is acrylic acid or methacrylic acid, the (poly) alkylene glycol chain is the (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 (22) to (25), ^{the positions of R 22} and the COOH group of the unsaturated carboxylic acid-based monomer unit are drawn on the hydrogen atom side at the terminal, but R ^{22 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 (22) to (25), ^{whether the positions of the R 13} and COOH groups are on the hydrogen atom side or the sulfur atom side is randomly determined for each monomer unit.

[Residual of compound having active hydrogen (Z1)]
In the present specification, the residue of a compound having active hydrogen means a group having a structure obtained by removing active hydrogen from a compound having active hydrogen, and the active hydrogen means hydrogen to which alkylene oxide can be added. .. The residue of the compound having such active hydrogen may be one kind or two or more kinds.

Specific examples of the residue of the compound having active hydrogen include a polyhydric alcohol residue having a structure in which active hydrogen is removed from the hydroxyl group of the polyvalent alcohol, and active hydrogen being removed from the amino group of the polyvalent amine. Polyvalent amine residue having a structure, polyvalent imine residue having a structure obtained by removing active hydrogen from the imino group of polyvalent imine, and polyvalent amide having a structure obtained by removing active hydrogen from the amide group of a polyvalent amide compound. Residues and the like are suitable. Of the polyvalent amine residues, polyhydric alcohol residues, and polyvalent imine residues, polyalkyleneimine residues are preferable. That is, the residue of the compound having three or more active hydrogens is at least one polyvalent compound residue selected from the group consisting of a polyvalent amine residue, a polyalkyleneimine residue and a polyhydric alcohol residue. It is preferable to have.
The structure of the compound residue having active hydrogen may be any of a chain-like, branched-like, and three-dimensionally crosslinked structures.

Among the preferable specific examples of the residues of the compound having active hydrogen, the polyvalent amine (polyamine) may be a compound having an average of two or more amino groups in one molecule, for example, methylamine and the like. Alkylamines; alkyleneamines such as allylamines; aromatic amines such as aniline; homopolymers and copolymers obtained by polymerizing one or more monoamine compounds such as ammonia by a conventional method are suitable. Such a compound forms a polyvalent amine residue contained in the multi-branched (poly) alkylene glycol-based block copolymer.
Further, it may be a divalent or higher amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, or a polyamine obtained by polymerizing one or more of them. Such a polyamine usually has a primary amino group having an active hydrogen atom and a secondary amino group (imino group) in addition to the tertiary amino group in the structure.

The polyalkyleneimine may be a compound having an average of 3 or more imino groups in one molecule. For example, one or two kinds of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine and propyleneimine. A homopolymer, a copolymer, or the like obtained by polymerizing the above by a conventional method is suitable. Such a compound forms a polyalkyleneimine residue contained in the multi-branched (poly) alkylene glycol-based block copolymer. The polyalkyleneimine is three-dimensionally crosslinked by polymerization, and usually has a primary amino group having an active hydrogen atom and a secondary amino group (imino group) in addition to the tertiary amino group in the structure. become.
Among these, polyethyleneimine obtained by polymerizing ethyleneimine is more preferable from the viewpoint of the performance of the multi-branched (poly) alkylene glycol-based block copolymer.

The number average molecular weight of the polyvalent amine and the polyalkyleneimine is preferably 100 to 100,000, more preferably 300 to 50,000, still more preferably 600 to 10000, and particularly preferably 800 to 5000.

The polyhydric alcohol may be a compound containing an average of 3 or more hydroxyl groups in one molecule, but a compound composed of three elements of carbon, hydrogen and oxygen is preferable. Specifically, for example, polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, Sugars such as adonitol, arabitol, xylitol, mannitol and glucose, sugar alcohols such as glycit, sugar acids such as gluconic acid and the like are suitable. Such a compound forms a polyhydric alcohol residue contained in the multi-branched (poly) alkylene glycol-based block copolymer.
Among these, glycerin, polyglycerin, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, sorbitol, and sorbitan are more preferable from the viewpoint of industrial production efficiency.

[Method for producing the (poly) alkylene glycol-based block copolymer of the third preferred embodiment]
In the following, first, the methods for producing the (poly) alkylene glycol-based block copolymers (1) and (2) will be described, and then the above-mentioned (poly) alkylene glycol-based block copolymers (3) and (2) will be described. The manufacturing method of 4) will be described.

[Methods for producing (poly) alkylene glycol-based block copolymers (1) and (2)]
As an example of the method for producing the (poly) alkylene glycol-based block copolymers (1) and (2) of the third preferred form, a bond site containing a sulfur atom derived from thioacetic acid (or a metal salt thereof) is used. The case of producing the copolymer having the same will be described below.

The (poly) alkylene glycol-based block copolymer (1) and (2) according to the third preferred embodiment produce a ((poly) alkylene glycol-based block copolymer (2) at at least one terminal. In the case, a step of preparing a polymer chain (B) made of a (poly) alkylene glycol-based structural unit having a hydroxyl group terminal (at both ends) and performing a tosylation reaction on the hydroxyl group end (tosylation step). , A step of reacting thioacetic acid or a metal salt thereof to carry out a thioacetylation reaction (thioacetylation step), a step of hydrolyzing a thioacetyl group obtained by the thioacetylation step (hydrolysis step), and having a thiol group at the terminal ( It is produced by performing a step (block polymerization step) of block-polymerizing an unsaturated vinyl-based monomer using a radical polymerization initiator using a polymer chain (B) consisting of a poly) alkylene glycol-based structural unit as a chain transfer agent. be able to.
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 referred to as 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 tosylizing 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 constituent unit is obtained.
The thioacetylating agent and 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 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 (26) and (27) can be obtained.
The PAG (di) thiol compounds represented by the following formulas (26) and (27) are preferable as intermediates for producing the (poly) alkylene glycol-based block copolymers (1) and (2) according to the present invention, respectively. is there.
In the above hydrolysis step, the reaction conditions may be appropriately set so that the hydrolysis of the thioacetyl group proceeds.

(In formulas (26) and (27), R ¹⁰ , R ¹⁶ , and n1 are the same as above. AO represents an oxyalkylene group.)

Further, as will be described later, the (poly) alkylene glycol-based block copolymers (3) and (4) in the present invention can also be produced by a production method including the above-mentioned tosylation step, thioacetylation step, and hydrolysis step. .. In that case, the PAG (di) thiol compound obtained through the hydrolysis step is a compound having a structure represented by the following formulas (28) and (29).

(In equations (28) and (29), Z1, B, R ¹¹ , R ¹⁶ , n3, n4, p1, m1, and m2 are the same as above.)

[Block polymerization step]
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 copolymers (1) and (2) in the third preferred form can be produced easily, efficiently, and at low cost.
Among the unsaturated anionic monomers contained in the vinyl-based monomer component, it is preferable that the unsaturated carboxylic acid-based monomer (monomer (a)) forming the polymer chain (A) is 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 pH 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. 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 (manufactured by 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 anion-based monomers are added one after another to one end of the polyalkylene oxide moiety composed of an oxyalkylene group to form the (poly) alkylene glycol-based block copolymer of the third preferred form. To.

When a copolymer having a bond site derived from a residue containing a phosphorus atom is produced, 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 is produced. 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 by 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.

[Methods for producing (poly) alkylene glycol-based block copolymers (3) and (4)]
The method for producing the (poly) alkylene glycol-based block copolymers (3) and (4) according to the third preferred embodiment is a step of obtaining a polymer chain using a multi-branched (poly) alkylene glycol-based structural unit (first step). Step 1) and a step of polymerizing a vinyl-based monomer component containing an unsaturated anion-based monomer on a part or all of the terminal portions of the branched portion in the multi-branched (poly) alkylene glycol-based polymer (step 1). It can be produced by performing these steps in this order, including the second step).
The first step can be carried out by adding a polymer chain (B) consisting of a (poly) alkylene glycol-based structural unit to a compound having three or more active hydrogens.
The second step can be carried out in the same manner as the method for producing the (poly) alkylene glycol-based block copolymers (1) and (2) according to the present invention described above.

<Fourth preferred form>
The compound contained in the shrinkage reducing agent in the present invention has at least two ends of a linear or branched polyalkylene glycol chain having an organic residue exhibiting an adsorptive ability to at least one of a metal, a metal compound and a metal ion. In the bonded polyalkylene glycol compound, the organic residue is 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. The compound having the above is the fourth preferred form of the compound contained in the shrinkage reducing agent in the present invention.

A compound in which an organic residue is bonded to at least two ends of a linear or branched polyalkylene glycol chain according to the fourth preferred embodiment (hereinafter, also referred to as an organic residue-containing polyalkylene glycol compound) is poly. Other structural sites may be included as long as they have at least three structural sites of an alkylene glycol 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 having an unmodified end (a form in which 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, the 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 preferred form may have any of a carbonyl group, a hydroxyl group, an amino group, a phosphate group or a silane group among the functional groups. preferable. 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 phosphate 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.

A compound in which an organic residue is bonded to at least two ends of the linear or branched polyalkylene glycol chain of the fourth preferred form has a compound having 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 below.

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 ethylenediaminetetramine-N, N, N', N'', N''', N'''-hexaacetic 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; 2,3-dimercaptopropanol, unithiol, thioglycolic acid, β-mercaptopropionic acid, dimercapto oxalic acid , Aminoethyl mercaptans, thiooxalic acids, thiosamines such as cysteamines; sulfurs such as sodium diethyldithiocarbamate, thiourea, thiocarbazide, thiosemicarbadides; 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 glycols, modified polyalkylene glycols described later, compounds having a functional group capable of reacting with polyalkylene glycols 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. Examples of these include reacting an epoxy group such as polyethylene glycol diglycidyl ether with an amino group such as aspartic acid and 3-hydroxytyramine to bond them. Further, if necessary, the hydroxyl group of the compound giving the organic residue, the hydroxyl group of 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, if necessary. By introducing an amino group, a carboxyl group, an epoxy group, etc., and further reacting these functional groups with a compound that newly imparts the above organic residue, a polyalkylene glycol having organic residues 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 (30). This compound is obtained, for example, by the Mannich reaction of α, ω-diaminopolyalkylene glycol, formaldehyde, and phosphorous acid.
R ²³ R ²⁴ NCH ₂ CH ₂ (OA ¹ ) _n6 CH ₂ CH ₂ R ²⁵ R ²⁶ (30)
(In the formula, A ¹ represents the same or different alkylene group having 2 to 18 carbon atoms. R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently −CH _2- PO (OM ⁴ _q2 ). Represents ₂ or -R ^{27. At} least one of ^{R 23} and R ²⁴ _{is -CH 2-} PO (OM ⁴ _q2 ) ₂ , and at least one of ^{R 25} and R ²⁶ _{is -CH 2-} PO (OM ^4). ) _2. R ²⁷ 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. The group represents 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.)

^{A 1} in the above formula (30) is preferably an ethylene group and / or a propylene group, and more preferably an ethylene group.
^{R 27} in the above formula (30) is preferably an alkyl group having 1 to 15 carbon atoms, and 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 fourth preferred form of the organic residue-containing polyalkylene glycol compound, 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 , Polyalkylene glycol forming a polyalkylene glycol chain / a compound giving an organic residue used for forming an organic residue = 99 to 1/1 to 99 is preferable. It is more preferably 98 to 10/2 to 90, still more preferably 97 to 20/3 to 80, and particularly preferably 97 to 30/3 to 70.

In the fourth preferred form of the organic residue-containing polyalkylene glycol compound, the monomer component that is the raw material of the compound is a polyalkylene glycol that forms a polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound. It is a compound that gives an organic residue used to form an organic residue, and 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 to the number of moles of the compound giving the above is preferably 99 to 1/1 to 99. More preferably, it is 75 to 3/25 to 97. More preferably, it is 50 to 3/50 to 97, even more 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 preferred 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 preferred 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 moles added is more preferably 25, further preferably 40, and particularly preferably 50. 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 250.

In the above-mentioned fourth preferred form of the organic residue-containing polyalkylene glycol compound, the weight average molecular weight (Mw) of the polyalkylene glycol forming the polyalkylene glycol chain is not particularly limited, but is, for example, 1000 to 1000000. Is preferable. It is more preferably 2000 to 50000, still more preferably 2000 to 40,000, and particularly preferably 3000 to 35000.
The degree of dispersion 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 preferred 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. it can.

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 and 10 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 ions adsorbed by the organic residues are 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 groups 8, 10, 11, 12, 13 and 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 preferred form>
The fact that the compound contained in the shrinkage reducing agent in the present invention is a polyamine compound having an acid group-containing side chain is a fifth preferred form of the compound contained in the shrinkage reducing agent in the present invention.

The fifth preferred form of the polyamine compound is a compound having a structure in which active amine hydrogen of a polyamine compound having a primary and / or secondary amino group in the molecule is substituted with an acid group-containing side chain. 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 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 reaction of alkyleneimines with urea; polyamide polyesterpolyamines obtained by copolymerization of 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, 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 (Nitto Boseki 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 1000 to 50,000. At this time, if the molecular weight is less than 1000, 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, further preferably 2000 to 35,000, and most preferably 2000 to 30000.
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 acid group-containing side chain is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, or a side chain having a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic amine salt thereof.
The acid group-containing side chain is an acid having a structure in which a carboxyl group, a sulfonic acid group, or a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic amine salt is bonded to an atomic group that reacts with an amino group. It can be produced by reacting a group-containing compound with a polyamine compound.
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 acid group-containing compound include (meth) acrylic acid, maleic acid, and the like, and one or more of these can be used.

The amount of the acid group-containing compound used 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.

In order to form an acid group-containing side chain with an unsubstituted polyamine compound used for forming the polyamine compound having an acid group-containing side chain in the polyamine compound having the acid group-containing side chain of the fifth preferred form. The mass ratio of the acid group-containing compound used in 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 = It is preferably 99.9 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. It is more preferably 99.8 to 55 / 0.2 to 45, further preferably 99.7 to 60 / 0.3 to 40, and particularly preferably 99.7 to 65 / 0.3 to 35. ..

In the polyamine compound having an acid group-containing side chain of the fifth preferred form, the monomer component which is a raw material of the compound is an unsubstituted compound used for forming a polyamine compound having an acid group-containing side chain. A polyamine compound, an acid group-containing compound used for forming an acid group-containing side chain, and the number of moles of an unsubstituted polyamine compound used for forming a polyamine compound having an acid group-containing side chain. The ratio to the number of moles of the acid group-containing compound used for forming the acid group-containing side chain is preferably 99 to 1/1 to 99. It is more preferably 75 to 3/25 to 97, further preferably 50 to 3/50 to 97, and particularly preferably 30 to 4/70 to 96. Yes, most preferably 25-5 / 75-95.

The polyamine compound of the fifth preferred 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; Alkylphenol glycidyl ethers 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 kinds of 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. .. More preferably, it is 0.05 to 0.90 mol, further 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 (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 (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. These may be used alone or in combination of two or more.

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 are not particularly limited. 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 thereof 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 are 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.

<Other suitable forms>
Even compounds other than the above (I) to (V) can be used as the shrinkage reducing agent in the present invention as long as they satisfy the above conditions (1) and (2). For example, a compound in which a polyoxyalkylene chain is introduced into a copolymer of a vinyl aromatic, a diene or an α-olefin and an unsaturated dicarboxylic acid by esterification or amidation can be mentioned. Specifically, an amine having a polyoxyalkylene chain in maleic anhydride of a styrene / maleic anhydride copolymer; an isobutylene / maleic anhydride copolymer or an octadecene / maleic anhydride copolymer (Jeffamine; manufactured by Huntsman). Examples thereof include a compound in which the above-mentioned compound is introduced; a phosphate ester polymer having the phosphate ester-based monomer described in Patent No. 4717713 as a main constituent unit; and the like.

The air entraining agent contained in the water-hard material composition of the present invention is not particularly limited as long as it functions as an air entraining agent, and examples thereof include resin soap, saturated or unsaturated fatty acids or salts thereof, sodium hydroxystearate, and the like. 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 Examples thereof include esters or salts thereof, polyoxyethylene alkyl (phenyl) ether phosphate esters or salts thereof, protein materials, alkenylsulfosuccinic 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.

The water-hard material contained in the water-hard material composition of the present invention is not particularly limited as long as it has water-hardness or latent water-hardness, and for example, Portland cement such as ordinary Portland cement and early-strength Portland cement, or silica. Cement, fly ash cement, blast furnace cement, alumina cement, belite high content cement, various mixed cements; components of cement such as tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium iron aluminate; latent hydraulic hardness Examples include fly ash having. 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 blending ratio of the hydraulic material 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 100% by weight of the entire hydraulic material composition. It is more preferably 0.01 to 10% by weight, and even more preferably 0.01 to 3% by weight.

When the hydraulic material composition of the present invention contains water, the mixing ratio of water is not particularly limited, and for example, it is preferably 10 to 80% by weight with respect to the hydraulic material. 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 water-hard material composition of the present invention is a cement composition containing cement and the cement composition is used as mortar or concrete, conventionally known cement compositions are used as sands and stones to be blended in the cement composition. 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 aggregate 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.

If necessary, other materials may be blended in the hydraulic material composition. As the other material, the same material as the conventionally known cement composition can be used, and is not particularly limited, and for example, a water reducing agent, a defoaming agent, a hardening accelerator, a retarding agent, a rust preventive, an expanding material, Examples thereof include silica fume, blast furnace slag, fly ash, silica powder, and fibrous materials such as steel fiber and glass fiber. The blending amount of these materials may be the same as that of a conventionally known cement composition, and is not particularly limited.

When the hydraulic material composition contains a water reducing agent, the content of the water reducing agent 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 10 parts by weight, and even more preferably 0.01 to 3 parts by weight.

The 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 is, for example, a monovalent metal salt, a divalent metal salt, an ammonium salt, or an organic amine of lignin sulfonic acid. Ligno sulfonates such as salts; polyol derivatives; formaline condensates of naphthalene sulfonate; alkenyl ether-based monomers and unsaturated carboxylic acids obtained by adding ethylene oxide or the like to unsaturated alcohols such as 3-methyl-3-buten-1-ol. A single amount containing a copolymer or a salt thereof obtained from a monomer containing a system monomer, a (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester system monomer, and a (meth) acrylic acid system monomer. Examples thereof include a polymer obtained from a polymer or a polymer having a polyoxyalkylene group such as a salt thereof and an anionic group. Among these water reducing agents, a lignin sulfonate, a polymer having a polyoxyalkylene group and an anionic group is preferable.

When the hydraulic material composition contains a defoaming agent, the content of the defoaming agent is preferably 0.0001 to 0.5 parts by weight in terms of solid content with respect to 100 parts by weight of the hydraulic material. .. It is more preferably 0.0005 to 0.1 parts by weight, and even more preferably 0.001 to 0.05 parts by weight.

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, and is, 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 an alkylene oxide to an 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 sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate. 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.

The method for producing the hydraulic material composition of the present invention is not particularly limited, and the composition may be a composition containing a hydraulic material, a shrinkage reducing agent, and an air entraining agent. A method of adding and mixing can be used by various commonly used methods described in JP-A-2008-503432 and JP-A-2008-512268. 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 an air entraining agent with water and mixing them with a hydraulic material to produce a hydraulic material composition (b) After powdering the shrinkage reducing agent and the air entraining agent, Method of producing a hydraulic material composition by mixing with a hydraulic material and adding water to the obtained mixture (c) A shrinkage reducing agent and an air entraining agent are added at the time of producing the hydraulic material, and the shrinkage reducing agent and the air entraining agent are entrained. Method of producing a hydraulic material composition by adding water after producing a hydraulic material containing an agent (d) In the method of (c) above, a shrinkage reducing agent and an air entraining agent at the time of producing a hydraulic material. As a method of adding crushing aid or crushing aid, a shrinkage reducing agent and an air entraining agent are added at the same time (when the hydraulic material is cement).
(E) A method of spraying and adding an aqueous solution containing a shrinkage reducing agent and an air entraining agent during transportation after manufacturing a hydraulic material.

The hydraulic material composition of the present invention has the above-mentioned structure and is excellent in both shrinkage reduction performance and freeze-thaw resistance, and is suitably used as a cement composition for constructing civil engineering / building structures and the like. be able to.

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 was measured as follows. The surface tension of the polymer was measured under the above-mentioned surface tension measurement condition (2).
<Molecular weight measurement (GPC analysis method)>
Equipment: Waters Alliance (2695)
Analysis software: Waters, Emper Professional + GPC option used Column: Tosoh Co., Ltd., TSKguardvolumes α + TSKgel α5000 + 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 creation: 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 91.0 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. with a nitrogen atmosphere. 123.8 parts of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added 23), 8.9 parts of methacrylic acid, 30.9 parts of water, 0.69 parts of 30% aqueous sodium hydroxide solution, and 3-mercapto as a chain transfer agent. A monomer aqueous solution containing 4.6 parts 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 7 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% aqueous sodium hydroxide solution to have a weight average molecular weight of 5200 and an acid content of 48.0 mol%. (Polymer 1) was obtained.
Here, the amount of acid means the mol% of the acid group-containing monomer out of 100 mol% of the total monomer component which is the raw material of the polymer. The same applies to the following polymers.
The surface tension of the 5% by mass aqueous solution of the polymer 1 was 62.0 mN / m.

(Production Example 2) Production of Polymer 2 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 20000 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., 6.9 parts of acrylic acid and 2.5 g of perbutyl D (trade name, manufactured by Nippon Oil & Fats Co., Ltd., di-t-butyl peroxide) were separately added for 1 hour. The mixture was continuously added dropwise, and then stirring was continued for 1 hour while maintaining 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 6.7 with a 30% aqueous sodium hydroxide solution. To obtain a polymer aqueous solution (polymer 2) having a weight average molecular weight of 21000 and an acid content of 90.6 mol%.
The surface tension of the 5% by mass aqueous solution of the polymer 2 was 59.7 mN / m.

(Production Example 3) Production of Polymer 3 (1. Tosylation step)
120.50 parts of methoxypolyethylene glycol (average number of moles of ethylene oxide added 75 (PGM75)), 9.146 parts of tosyl chloride (TsCl), triethylamine (Et ₃ N) in a glass reactor equipped with a stirrer. Was charged in 6.057 copies. 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 one-terminal tosylated products of PGM75 (PGM75-OTs).
(2. Thioacetylation step)
In a glass reactor equipped with a stirrer, 119.93 parts of PGM75-OTs and 5.120 parts of potassium thioacetate (CH ₃ COSK) were charged. After the reaction was carried out for 24 hours while stirring the inside of the reaction system, the salt was removed by filtration, and desolvation was carried out under reduced pressure to obtain a one-terminal thioacetylated product (PGM75-SAc) of PGM75.
(3. Hydrolysis step)
In a glass reactor equipped with a stirrer, 111.55 parts of PGM75-SAc and 140.00 parts of methanol were charged to dissolve PGM75-SAc, and 25.00 parts of 1N sodium hydroxide (NaOH) aqueous solution was added. After adding 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, desolvation was carried out under reduced pressure, and PGM was performed. A thiol compound was obtained.
(4. Block polymerization step)
For glass reactors equipped with thermometers, stirrers, dropping devices, nitrogen introducers and reflux cooling devices.
15.0 parts of ion-exchanged water was charged, the reactor was replaced with nitrogen under stirring, and 80 under a nitrogen atmosphere.
After raising the temperature to ° C., an aqueous solution (A) (acid aqueous solution) consisting of 6.40 parts of methacrylic acid (MAA) and 13.25 parts of ion-exchanged water (PW) was added dropwise over 4.0 hours to (A). ) Was started to be added dropwise, and at the same time, an aqueous solution (B) (PAG thiol aqueous solution) consisting of 45.00 parts of the PAG dithiol compound and 77.48 parts of ion-exchanged water was added dropwise over 4.0 hours. Further, at the same time as the dropping of (A) is started, 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 continuously, it 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 3450 and an acid amount of 83.3. A molar% copolymer aqueous solution (polymer 3) was obtained.
The surface tension of the 5% by mass aqueous solution of the polymer 3 was 62.2 mN / m.

(Production Example 4) Production of Polymer 4 (1. Production of both-terminal epoxidized poly (n = 227) ethylene glycol)
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 110.00 parts of poly (n = 227) ethylene glycol and 90.00 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 40. It was heated to ° C. 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 unreacted sodium hydride, THF is distilled off with an evaporator, the residue is added dropwise to 200 ml of diethyl ether, and the precipitate is collected and dried (). Both terminal epoxidized poly (n = 227) ethylene glycol was obtained.
(2. Production of polymer 4)
A glass reaction vessel equipped with a thermometer, a stirrer and a reflux condenser was charged with 105.00 parts of epoxidized poly (n = 227) ethylene glycol at both ends, heated to an internal temperature of 70 ° 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 4) having a weight average molecular weight of 10500 and an acid content of 66.7 mol%.
The surface tension of the 5% by mass aqueous solution of the polymer 4 was 60.4 mN / m.

(Production Example 5) Production of Polymer 5 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) 102.5 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. Here, 6.43 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, 10.21 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, 39.90 parts of acetic acid is added, and the pH is adjusted to 8.1 to adjust the weight average molecular weight to 10300 and the acid content to 88.6 mol%. 5) was obtained.
The surface tension of the 5% by mass aqueous solution of the polymer 5 was 69.1 mN / m.

(Comparative Production Example 1) Production of Comparative Polymer 1 An aqueous comparative polymer solution (comparative polymer 1) having an acid content of 81.0 mol% was obtained in the same manner as in Production Example 1 of JP-A-2007-76972.
The surface tension of the 5% by mass aqueous solution of Comparative Polymer 1 was 58.0 mN / m.

(Comparative Production Example 2) An aqueous comparative polymer solution (comparative polymer 2) having an acid content of 73.2 mol% was obtained in the same manner as in Reference Example 1 of Patent No. 3179022 for producing the comparative polymer 2.
The surface tension of the 5% by mass aqueous solution of the comparative polymer 2 was 63.1 mN / m.

(Comparative Production Example 3) Production of Comparative Polymer 3 An aqueous comparative polymer solution (comparative polymer 3) having an acid content of 82.1 mol% was obtained in the same manner as in Example 1-3 of Japanese Patent No. 3683176.
The surface tension of the 5% by mass aqueous solution of the comparative polymer 3 was 60.5 mN / m.

(Comparative Production Example 4) Production of Comparative Polymer 4 An aqueous comparative polymer solution (comparative polymer 4) having an acid content of 40.6 mol% was obtained in the same manner as in Example 1-7 of Japanese Patent No. 3683176.
The surface tension of the 5% by mass aqueous solution of the comparative polymer 4 was 61.3 mN / m.

(Comparative Production Example 5) Production of Comparative Polymer 5 108.7 parts of polyethylene glycol having a weight average molecular weight of 1000 was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser, and a nitrogen stream was introduced. It was heated to 120 ± 5 ° C. below and melted. Next, while maintaining the temperature at 120 ± 5 ° C., 47.03 parts of acrylic acid and 2.5 g of perbutyl D (trade name, manufactured by Nippon Oil & Fats Co., Ltd., di-t-butyl peroxide) were separately added for 1 hour. The mixture was continuously added dropwise, and then stirring was continued for 1 hour while maintaining 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 6.7 with a 30% aqueous sodium hydroxide solution. To obtain an aqueous comparative polymer solution (comparative polymer 5) having an acid content of 85.7 mol%.
The surface tension of the 5% by mass aqueous solution of the comparative polymer 5 was 63.8 mN / m.

(Comparative Production Example 6) Production of Comparative Polymer 6 (1. Tosylation Step)
In a glass reactor equipped with a stirrer, 33.33 parts of methoxypolyethylene glycol (MPEG1000) having an average addition molar number of 25 ethylenexide, 6.867 parts of tosyl chloride (TsCl), and triethylamine (Et ₃ N). A tosylated product of MPEG1000 (MPEG1000-OTs) was obtained in the same manner as in the tosylation step of Production Example 3 except that 4.556 parts and 200.0 parts of dichloromethane were used.
(2. Thioacetylation step)
The same method as the thioacetylation step of Production Example 3 except that 33.12 parts of MPEG1000-OTs and 3.907 parts of potassium thioacetate (CH _{3 COSK) were used in a glass reactor equipped with a stirrer.} A thioacetylated product of MPEG1000 (MPEG1000-SAc) was obtained.
(3. Hydrolysis step)
PAG in the same manner as in the hydrolysis step of Production Example 3 except that 32.215 parts of the synthesized MPEG1000-SAc and 50.00 parts of MeOH were used in a glass reactor equipped with a stirrer. A monothiol compound was obtained.
(4. Block polymerization step)
For glass reactors equipped with thermometers, stirrers, dropping devices, nitrogen introducers and reflux cooling devices.
15.0 parts of ion-exchanged water was charged, the reactor was replaced with nitrogen under stirring, and 80 under a nitrogen atmosphere.
After raising the temperature to ° C., there is an aqueous solution (A) (acid aqueous solution) consisting of 5.774 parts of methacrylic acid (MAA), 0.962 parts of a 30% sodium hydroxide aqueous solution, and 23.906 parts of ion-exchanged water (PW). Aqueous solution (B) (PAG thiol aqueous solution) consisting of 3.800 parts of PAG monothiol compound and 8.740 parts of ion-exchanged water was added at the same time when (A) was started to be added dropwise over 4.0 hours. Dropped over time. Further, at the same time as the dropping of (A) is started, 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 continuously, it was cooled to complete the polymerization, and neutralized to pH 7.1 with a 30% aqueous sodium hydroxide solution to have a weight average molecular weight of 2980 and an acid amount of 95.5. An aqueous solution of a molar% comparative copolymer (comparative polymer 6) was obtained.
The surface tension of the 5% by mass aqueous solution of the comparative polymer 6 was 62.1 mN / m.

(Measurement of values of conditions (1) and (2) in the present invention)
Prepare a JASS 5 M402 compliant mortar with the following composition, and use the following 15-stroke flow and 0-stroke flow measurement methods to measure the above polymers 1 to 5, comparative polymers 1 to 6, and commercially available weight average molecular weight 4500. And for polyethylene glycol (PEG4500) having an acid content of 0 mol%, the conditions (1) in the present invention: (15 stroke flow value of the compound-containing mortar composition) / (15 stroke flow value of the mortar not containing the compound) ×. 100, Condition (2): (Ratio of 15 stroke flow values after 2 hours) / (Ratio of 15 stroke flow values after 10 minutes) × 100 was measured. The results are shown in Table 1. (I) to (V) in Table 1 describe the classification of the polymer in the present invention described above, and each classification is as follows.
When the polymer (shrinkage reducing agent) was added to the JASS 5 M402 compliant mortar, 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
Add a defoamer (Master Air 404 (manufactured by BASF Japan)) so that the amount of mortar air is ± 3% without the addition of 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 defoamer diluted with water so as to have a solid content of 0.1% with respect to 100 parts by weight of cement was placed in a kneading bowl, and 450 g of ordinary Portland cement was added thereto. Was immediately put in and 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 the 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, the 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.

(Shrinkage reduction performance evaluation)
The shrinkage reduction performance of the polymers 1 to 5 and the comparative polymers 1 to 6 was evaluated by the following method. The results are shown in Table 2. The classification of polymers in Table 2 is the same as in Table 1.
<Evaluation of shrinkage reduction performance>
(Creation of specimen)
The specimen (4 x 4 x 16 cm) used for the evaluation of shrinkage reduction performance uses a predetermined amount of additives shown in Table 2 and kneaded according to the above-mentioned <Mortar composition kneading>, and uses JIS. It was carried out according to the method of Annex 2 of R5201.
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.

From the results in Table 2, it was confirmed that the polymer satisfying the above conditions (1) to (3) exerts an excellent effect as a shrinkage reducing agent for the cement composition. In Table 2, polymers having different structures are used, but in any of the polymers, those satisfying the above conditions (1) to (3) exhibit excellent shrinkage reduction performance. It was confirmed that it is meaningful to satisfy the above conditions (1) to (3).

(Concrete test)
Using various compounds synthesized in the production example and a commercially available shrinkage reducing agent, the composition obtained by blending other admixtures was evaluated for length change and compressive strength in concrete. Table 3 shows the compounds and other admixtures used in the evaluation. In addition, concrete kneading and each evaluation were carried out as follows.

(1) Concrete test Concrete composition shown below Unit cement amount: 309 kg / m ³
Unit water volume: 170 kg / m ³
Unit fine aggregate amount: 822 kg / m ³
Unit coarse aggregate amount: 942 kg / m ³
(Water-cement ratio (W / C): 55%, fine aggregate ratio (s / a): 48.0%)
Each material was weighed so that the amount of kneading was 30 L, and the materials were kneaded using a forced biaxial kneading mixer. As the cement, ordinary Portland cement (specific gravity 3.16) manufactured by Taiheiyo Cement Co., Ltd. was used. At this time, Kakegawa land sand and Kimitsu land sand were used for the fine aggregate, and Ome hard sandstone was used for the coarse aggregate. Further, a commercially available air amount adjusting agent (AE agent and defoaming agent; see Table 3) was used to adjust the air amount of the concrete to 5 ± 1%. Further, a polycarboxylic acid-based high-performance AE water reducing agent was appropriately added to adjust the slump to 18 ± 2 cm. The composition of each admixture is shown in Table 4.

(2) Mixing of materials The coarse aggregate, fine aggregate and cement are put into a mixer and kneaded for 10 seconds, then the rotation is stopped, and the compound (A), water reducing agent (B), AE agent (C) and defoaming are stopped. Water containing foaming agent (D) was added and kneaded for 60 seconds, then the rotation was stopped to scrape off the mortar on the stirring blade and shaft, and after kneading again for 60 seconds, the concrete was taken out from the mixer and evaluated. did.
(3) Evaluation of fresh concrete For the obtained fresh concrete, the slump value and the amount of air were measured by the following methods.
Slump value: JIS A 1101-1998
Air volume: JIS A 1128-1998
(4) Evaluation of drying shrinkage reduction property Kneading of concrete was carried out by the methods of items 1 and 2 above. After confirming that the slump and the amount of air were the predetermined values, a concrete specimen (10 × 10 × 40 cm) for evaluation of drying shrinkage reduction was prepared and the length change was measured according to JIS A1129.
Silicone grease was applied to the mold in advance to stop water and make it easy to remove the mold. In addition, gauge plugs were attached to both ends of the specimen. The mold in which the concrete obtained by kneading was poured was stored at 20 ° C. for initial curing. After 1 day, it was demolded and then cured in still water at 20 ° C. for 6 days (underwater curing).
A dial gauge (manufactured by West Japan Railway Company) was used in accordance with JIS A1129. 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 ° C. and a humidity of 60%, and the length was measured in a timely manner.
The evaluation of shrinkage reduction was carried out by calculating the length change ratio by the following formula (i).
Length change ratio (%) = (L2 / L1) x 100 (i)
L1: Shrink strain of the concrete specimen to which the shrink reduction agent is added L2: The shrinkage strain length change ratio of the concrete (reference concrete) to which the shrink reduction agent is not added is smaller, the better the shrinkage reduction performance is.

(5) Evaluation of freeze-thaw resistance The obtained fresh concrete was placed in a 10 × 10 × 40 cm specimen mold, sealed at 20 ° C. for 2 days, and then demolded. After demolding, it was cured in still water at 20 ° C. for another 5 days, and then freeze-thaw resistance was evaluated.
The evaluation of freeze-thaw resistance was carried out by measuring the primary resonance frequency and the specimen weight according to the method A in JIS A1148-2001 and according to JIS A1127-2001 every 30 cycles.
At this time, the freeze-thaw resistance every 30 cycles is the primary resonance frequency at the end of each cycle with respect to the primary resonance frequency before the start of the freeze-thaw cycle (0 cycle), as shown by the following formula (ii). The relative dynamic elastic modulus was calculated from and evaluated. The maximum freeze-thaw cycle was 300 cycles, and if the relative dynamic elastic modulus became 60% or less before 300 cycles, the evaluation was completed at that time. The final freeze-thaw resistance was evaluated by calculating the durability index represented by the following formula (iii). The closer the relative dynamic elastic modulus and the durability index are to 100, the better the freeze-thaw resistance is.
The relative dynamic modulus ^{_{(%) = (f n 2}} / f 0 2) × 100 (ii)
f _n : Primary resonance vibration (Hz) after n cycles of freeze-thaw
f ₀ : Primary resonance vibration (Hz) of 0 cycle of freeze-thaw
Durability index = (P × N) / 300 (iii)
P: Relative elastic modulus (%) during freeze-thaw N cycle
N: Table 5 shows the concrete physical property evaluation results for each admixture combination, whichever is smaller, the number of freeze-thaw cycles in which the relative dynamic elastic modulus (%) is 60% or less, or 300 cycles.

Comparing the results of Examples 1 to 5 and Comparative Examples 1 to 5, the polymer (shrinkage reducing agent) satisfying the above conditions (1) to (3) and the air entraining agent (AE agent) were mixed in a predetermined ratio. It was confirmed that the composition containing the mixture was excellent in both shrinkage reduction performance and freeze-thaw resistance.

Claims (1)

A hydraulic material composition containing a hydraulic material, a shrinkage reducing agent and an air entraining agent.
The shrinkage reducing agent contains at least one compound selected from the group consisting of the following (I) to (V) satisfying the following conditions (1) to (3).
The content of the air entraining agent is 0.002 parts by weight or more with respect to 100 parts by weight of the hydraulic material.
A hydraulic material composition characterized in that the mass ratio of the shrinkage reducing agent and the air entraining agent is 99.98 / 0.02 to 80/20.
(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 compound. Ratio of values: (15 stroke flow value of the compound-containing mortar composition) / (15 stroke flow value of the mortar not containing the compound) × 100 is 120 or less (2) JASS 5 M402 compliant mortar not containing the compound The ratio of the 15-stroke flow value 2 hours after the start of kneading and the 15-stroke flow 10 minutes 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%. Ratio to value ratio: (ratio of 15 stroke flow values after 2 hours) / (ratio of 15 stroke flow values after 10 minutes) x 100 is 110 or less (3) Monomer component which is a raw material of the compound The ratio of the compound having an acid group in 100 mol% is 1 to 99 mol%.
(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 of 0 , q represents a number of 1 , and n represents the average number of moles of oxyalkylene group added. The structural unit (I) represented by (a number from 1 to 300) 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, an organic amine group or a hydrocarbon group). The mass ratio of the structural unit (II) and the other structural unit (III) is structural unit (I) / structural unit (II) / structural unit (III) = 98 to 85/2 to 15/0 to 13. Polymer (II):
The following formula (3);
W- (R ⁹ O) _r- Y (3)
(In the formula (3), R ⁹ O represents the same or different oxyalkylene group having 2 to 18 carbon atoms. R represents the average number of moles of the oxyalkylene group added, and is a number of 1 to 2000. .W and Y are the same or different, represent a hydrogen atom or a methyl group.) Ri Na ethylenically unsaturated monomer to the polyether compound represented by graft polymerization, the said ethylenically unsaturated monomer Polymer (III) in which the unsaturated carboxylic acid-based monomer in the body is 0.1 to 30% by weight based on the polyether compound:
Possess an ethylenically unsaturated monomer component derived from the polymer chain (A) and the end of the (poly) alkylene glycol chain (B) are bonded via a binding site (X) structure,
The number of moles of the unsaturated anion-based monomer in the ethylenically unsaturated monomer component forming the polymer chain (A), the number of moles of the polyalkylene glycol chain (B), and the unsaturated anion-based single the ratio of the moles of vinyl monomer other than dimer Ru 65-95 / 35-5 / 0-30 der (poly) alkylene glycol 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 organic residues may have a carbonyl group, a hydroxyl group, an amino group, a thiol group, phosphate group, at least one functional group selected from the group consisting of phosphorous acid and silane groups,
The mass ratio of the polyalkylene glycol forming the polyalkylene glycol chain to the compound giving the organic residue used to form the organic residue forms the polyalkylene glycol / organic residue forming the polyalkylene glycol chain. Compound giving the organic residue used for = 98-10 / 2-90 (V):
A polyamine compound having an acid group-containing side chain .
The polyamine compound is a compound having a structure in which active amine hydrogen of a polyamine compound having a primary and / or secondary amino group in the molecule is replaced with an acid group-containing side chain.
The mass ratio of the unsubstituted polyamine compound before the active amine hydrogen is replaced with the acid group-containing side chain to the acid group-containing compound used for forming the acid group-containing side chain is the unsubstituted polyamine compound / acid group-containing compound. = 99.7 to 65 / 0.3 to 35