阅读说明：本技术 水泥用添加剂、水泥混合剂、水泥组合物、成型体、以及成型体的强度提高方法 (Cement additive, admixture for cement, cement composition, molded article, and method for improving strength of molded article ) 是由 高山猛 石崎邦彦 阪本繁 于 2020-03-24 设计创作，主要内容包括：提供一种混凝土用添加剂,所述混凝土用添加剂即使添加,在浇注时的初期水泥组合物的粘性也低,另外流动性高,另外,通过添加,混凝土等的长期强度提高。一种水泥用添加剂,其含有吸水性树脂,其中,所述吸水性树脂是将含有非离子型非交联性单体50摩尔％以上及非离子型交联性单体0.1摩尔％以上的单体混合物进行聚合而成的,在所述单体混合物中,阴离子型单体的含量为20摩尔％以下。(Provided is an additive for concrete, which, even when added, has a low viscosity and a high fluidity in the initial stage of casting of a cement composition, and which, when added, improves the long-term strength of concrete and the like. An additive for cement, comprising a water-absorbent resin, wherein the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer, and the content of an anionic monomer in the monomer mixture is 20 mol% or less.)

1. An additive for cement which comprises a water-absorbent resin,

the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer,

the content of the anionic monomer in the monomer mixture is 20 mol% or less.

2. The additive for cement according to claim 1, wherein,

the water absorption capacity of the water-absorbent resin is lower than 20g/g after the water-absorbent resin is soaked in an aqueous solution with pH of 12.9 at 25 ℃ for 2 hours, wherein the aqueous solution with pH of 12.9 is CaSO₄·2H₂O 1.72g、Na₂SO₄6.96g、K₂SO₄4.76g, 7.12g of KOH and 979.4g of deionized water.

3. The additive for cement according to claim 1 or 2, wherein,

the water-absorbent resin has a water absorption capacity of 20g/g or more after being immersed in the aqueous solution having a pH of 12.9 at 25 ℃ for 28 days.

4. The additive for cement according to any one of claims 1 to 3, wherein,

90 mass% or more of the water-absorbent resin is in the range of 45 to 850 μm.

5. The additive for cement according to any one of claims 1 to 4,

the nonionic non-crosslinkable monomer is water-soluble.

6. The additive for cement according to any one of claims 1 to 5, wherein,

the nonionic non-crosslinkable monomer contains a (meth) acrylamide monomer.

7. An admixture for cement comprising the additive for cement as defined in any one of claims 1 to 6 and a cement dispersant.

8. The admixture for cement according to claim 7, wherein,

the cement dispersant is a polycarboxylic acid dispersant.

9. A cement composition comprising the additive for cement as defined in any one of claims 1 to 6 and cement.

10. The cement composition according to claim 9,

the cement composition further contains a cement dispersant.

11. The admixture for cement according to claim 10, wherein,

the cement dispersant is a polycarboxylic acid dispersant.

12. A cement composition comprising a water-absorbent resin and cement, wherein,

the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer, wherein the content of an anionic monomer in the monomer mixture is 20 mol% or less.

13. A molded article obtained by molding the cement composition according to any one of claims 9 to 12.

14. A method for improving the strength of a molded article obtained by molding a cement composition containing cement, wherein,

the method comprises the following steps: the cement composition is made to contain the additive for cement as defined in any one of claims 1 to 6.

15. A aggregate composition comprising the additive for cement as defined in any one of claims 1 to 6 and an aggregate.

Technical Field

The present invention relates to an additive for cement, an admixture for cement, a cement composition, a molded article, and a method for improving the strength of a molded article.

Background

Cement is widely used in civil engineering and construction sites, and cement compositions such as cement paste obtained by adding water to cement, mortar obtained by mixing sand as a fine aggregate with cement, and concrete obtained by mixing gravel with cement are used for various purposes such as structural materials, foundations, refractory walls, and the like, and the amount thereof is also large. These cement compositions are formed into a molded body by coagulation and solidification of cement through hydration reaction between the cement and water.

Additives for cement are added to cement compositions for the purpose of improving various properties. As such an additive, a water-absorbent resin is known. For example, patent document 1 discloses a water-absorbent resin obtained by adding a monomer component containing a sulfonic acid monomer to a cement composition and polymerizing the monomer component. By adding such a water-absorbent resin, the evaporation rate of water from the cement composition becomes slow at the initial stage of application, and cracks are not generated.

Further, patent document 2 discloses the following technique: in the case of adding a water-absorbent resin to a cement composition, since transportation time is required when fresh concrete before curing is transported from a factory for producing fresh concrete to a construction site, the water-absorbent resin reaches a saturated water absorption amount during transportation, and in view of such a problem, a water-absorbent resin obtained by coating the surface of a water-absorbent resin with a slow-soluble/hydrolyzable resin is used as an additive for cement.

Further, as a conventional technique relating to an additive for cement, there are patent documents 3 to 5.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 63-291840

Patent document 2: japanese laid-open patent publication No. 1-261250

Patent document 3: japanese laid-open patent publication No. H09-002854

Patent document 4: japanese laid-open patent publication No. 10-101392

Patent document 5: japanese laid-open patent publication No. 10-1343

Disclosure of Invention

One of the most important properties of the properties of a molded article obtained by molding a cement composition is strength. The intensities are roughly classified into early-stage intensities and long-term intensities. The early strength indicates the strength mainly for several days during curing, and when the early strength is high, the construction period is shortened or the labor is saved. On the other hand, the long-term strength indicates the strength mainly after 28 days during curing, and is directly related to the durability of concrete, and is an indispensable performance for a structure. Therefore, it is very important that the long-term strength of a molded article obtained by molding the cement composition is high.

The fresh concrete before curing is transported from a factory for producing fresh concrete to a construction site, pumped and fed by a pump at a casting site, and filled in a mold frame. When the fluidity of the cement composition is too low or the viscosity is too high at the time of pumping, there is a problem that the cement composition is clogged in the pipe when a long time is required for the transportation or the transportation is serious. Therefore, from the viewpoint of workability, the cement composition is preferably low in viscosity and high in fluidity at the time of casting.

Accordingly, an object of the present invention is to provide an additive for cement which has low viscosity and high fluidity in a cement composition at the initial stage of addition such as at the time of casting, and which improves the long-term strength of a molded article such as concrete by addition.

The additive for cement comprises a water-absorbent resin, wherein the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer, and the content of an anionic monomer in the monomer mixture is 20 mol% or less.

Detailed Description

< additive for cement >

A first embodiment of the present invention is an additive for cement, which contains a water-absorbent resin, wherein the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer, and the content of an anionic monomer in the monomer mixture is 20 mol% or less.

According to the additive for cement of the present embodiment, the viscosity of the cement composition at the initial stage is not easily changed by the addition. Therefore, the cement composition can be easily handled during casting, and can be easily pumped, thereby improving workability. In addition, the additive for cement according to the present embodiment improves the long-term strength of a molded body such as concrete after a long-term curing period (for example, after 28 days) by adding the additive.

By using the additive for cement of the present embodiment, the initial cement composition has high fluidity and low viscosity, while the long-term strength of the molded article is significantly improved. This excellent effect is thought to be due to: the water-absorbent resin of the present invention does not exhibit high water absorption performance immediately after the addition of water (for example, up to about 2 hours), exhibits water absorption capacity with the lapse of time, and exhibits high water absorption performance with the lapse of time.

The water-absorbent resin used in the first embodiment has an anionic monomer content of 20 mol% or less in the monomer mixture. When the content of the anionic monomer exceeds 20 mol%, the water absorption performance starts to be exhibited in an initial stage, for example, within 5 minutes after water is added (see comparative production example 1 described later). However, the water is adsorbed on the water-absorbent resin, so that the viscosity of the cement composition is rapidly increased, and the amount of the dispersant to be added is required to be greatly increased in order to improve the fluidity of the cement composition (comparative examples 9 to 16 described later). On the other hand, in the monomer mixture, the water absorption performance in the initial stage, for example, 5 minutes after water addition is not so much improved by setting the content of the anionic monomer to 20 mol% or less, the content of the nonionic non-crosslinkable monomer to 50 mol% or more, and the content of the nonionic crosslinkable monomer to 0.1 mol% or more. Further, the water-absorbing property does not exhibit a sharp level even after 2 hours of addition (see examples described later). Therefore, the water absorption amount of the water in the cement composition by the water-absorbent resin is low, and the viscosity and fluidity of the cement composition at the initial stage of the addition are maintained by adding a small amount of the cement dispersant. Therefore, the efficiency of the operation and the pumping operation of the operator can be smoothly performed. On the other hand, the present inventors found that: the long-term strength of the molded article is improved by adjusting the content of the anionic monomer to 20 mol% or less, the content of the nonionic non-crosslinkable monomer to 50 mol% or more, and the content of the nonionic crosslinkable monomer to 0.1 mol% or more in the monomer mixture. The water-absorbent resin of the present embodiment slowly absorbs ambient water from the time of casting to the time of curing because it slowly exhibits water absorption performance. This prevents the escape of moisture from the molded article. Further, since cement develops strength by hydration reaction, when the water content is insufficient, sufficient reaction cannot be performed, and the strength cannot be developed sufficiently as expected. It is considered that the hydration rate of cement is improved and the strength of concrete is improved by accumulating water in the water-absorbent resin after casting and supplying water from the water-absorbent resin to the remaining non-hydrated compound during curing. In view of the fact that water absorption performance is exhibited by repulsion of anionic groups in anionic monomers constituting a water-absorbent resin, it is a very unexpected fact that even a polymer having a small content of anionic monomers can exhibit high water absorption performance. The detailed mechanism of the polymer mainly composed of the nonionic monomer is not clear as to how the polymer can exert the water absorbing performance over time.

Next, the cement additive will be described in detail.

In the present specification, "X to Y" indicating a range means "X or more and Y or less".

In the present specification, "acid (salt)" means "acid and/or salt thereof". "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid".

[ Water-absorbent resin ]

In the present specification, the term "water-absorbent resin" means: a polymer gelling agent having a water-swelling capacity (CRC) of not less than 5g/g as defined in ERT441.2-02 and a soluble component of not more than 50% by mass. "ERT" is an abbreviation for the measurement method of water-absorbent resin (EDANA Recommendated Test Methods) of European standards (substantial world standards) established by the European Nonwovens Association (abbreviation for European Disposities and Nonwovens associates). In the present specification, unless otherwise specified, the physical properties of the water-absorbent resin were measured according to ERT 2002 edition.

The water-absorbent resin preferably has a water absorption capacity of less than 20g/g, more preferably less than 18g/g, and still more preferably less than 17.0g/g, after being immersed in 50mL of a pH12.9 aqueous solution at 25 ℃ for 2 hours. By having such characteristics, the cement additive has low viscosity at the initial stage of addition, high fluidity and excellent workability. The lower the water absorption capacity after immersion in an aqueous solution of pH12.9 at 25 ℃ for 2 hours, the lower the limit is not particularly limited, but usually 5g/g or more.

In the specification, the aqueous solution with pH of 12.9 is CaSO₄·2H₂O 1.72g、Na₂SO₄ 6.96g、K₂SO₄4.76g of aqueous solution, 7.12g of KOH and 979.4g of deionized water. The aqueous solution having a pH of 12.9 is a cement simulant simulating a case where the aqueous solution becomes a strong base when cement is contained. Therefore, the behavior of the water-absorbent resin when water is added to a cement composition containing the additive for cement can be simulated by using the aqueous solution.

The water absorption capacity of the water-absorbent resin after immersion in an aqueous solution having a pH of 12.9 at 25 ℃ for 28 days is, for example, 10g/g or more, and from the viewpoint of improving the long-term strength, it is preferably 20g/g or more, more preferably 30g/g or more, still more preferably 31g/g or more, and particularly preferably 35g/g or more. The higher the water absorption capacity after immersion in an aqueous solution of pH12.9 at 25 ℃ for 28 days, the higher the water absorption capacity, and the upper limit thereof is not particularly limited, but it is usually 50g/g or less, preferably 45g/g or less.

The water-absorbent resin is preferably a powder, and the shape of the powder may be a sphere or an aggregate thereof, or an amorphous shape (crushed shape) obtained by subjecting a hydrogel or a dried polymer to a crushing step, but is preferably an amorphous shape (crushed shape).

From the viewpoint of further improving the long-term strength, the particle size distribution of the water-absorbent resin (powder) is preferably such that 90 mass% or more thereof is in the range of 45 to 850. mu.m, more preferably 100 to 850. mu.m, still more preferably 250 to 850. mu.m, yet still more preferably 250 to 700. mu.m, and yet still more preferably 250 to 600. mu.m. It is considered that the water-absorbent resin (powder) has a larger average particle diameter, so that the water-releasing property is improved and the long-term strength is further improved. Further, the average particle diameter of the water-absorbent resin (powder) is preferably not more than the upper limit in view of freeze-thaw resistance.

The mass Average Particle Diameter (D50) of the water-absorbent resin (powder) can be measured by the same method as that of "Average Particle Diameter and Distribution of Particle Diameter" disclosed in European patent No. 0349240. That is, 10g of the particulate water absorbing agent was classified using a JIS standard sieve (JIS Z8801-1(2000)) or a sieve having mesh openings of 850. mu.m, 710. mu.m, 600. mu.m, 500. mu.m, 420. mu.m, 300. mu.m, 212. mu.m, 150. mu.m, 106. mu.m, and 45. mu.m, and the mass of the water-absorbent resin remaining on each sieve and the mass of the water-absorbent resin passing through the entire sieve were measured. The particles were classified for 5 minutes by a vibration classifier (IIDA SIEVE SHAKER, TYPE: ES-65 TYPE, SER.No.0501), and the particle size distribution was obtained by plotting the residual percentage R on a logarithmic graph paper. The particle diameter corresponding to 50 mass% of R may be read as the mass average particle diameter (D50) and used as the average particle diameter.

The residual monomer content in the water-absorbent resin is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and still more preferably 400 mass ppm or less. When the amount of residual monomers is not more than the upper limit, the safety is high when the residual monomers are added to a cement composition. The residual monomer content is preferably as small as possible, and is usually 5 mass ppm or more.

The amount of residual monomers can be reduced by a conventionally known method, for example, by adding a reducing substance after polymerization. The residual monomer amount herein means the amount of the monomer remaining in the water-absorbent resin. Examples of the reducing substance include inorganic reducing agents such as phosphorus-based reducing agents and sulfur-based reducing agents (particularly, oxygen-containing sulfur-based reducing agents); ascorbic acid and other organic reducing agents.

The residual monomer amount was measured as follows: according to ERT410.2-02, 1.0g of a water-absorbent resin was added to 200ml of a 0.9 wt% aqueous sodium chloride solution, and the mixture was stirred at 500rpm for 1 hour, and the amount (unit; mass ppm) of the dissolved monomer after the stirring was measured by HPLC (high performance liquid chromatography).

The water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer. The monomer mixture refers to the total of polymerizable monomers forming the polymer as the main component of the water-absorbent resin, and the total of the monomers forming the polymer is 100 mol%. The monomer mixture contains at least a nonionic non-crosslinkable monomer and a nonionic crosslinkable monomer. Both the nonionic non-crosslinkable monomer and the nonionic crosslinkable monomer are polymerizable monomers (monomers having an unsaturated double bond). The nonionic crosslinkable monomer is, for example, a monomer having 2 or more unsaturated double bonds and serving to crosslink the main chains with each other.

The content of the anionic monomer in the monomer mixture is 20 mol% or less.

In other words, the water-absorbent resin has 50 mol% or more of a constituent unit derived from the nonionic crosslinkable monomer and 0.1 mol% or more of a constituent unit derived from the nonionic crosslinkable monomer, and the constituent unit derived from the anionic monomer is 20 mol% or less. It is considered that the molar ratio of the constituent unit derived from the nonionic non-crosslinkable monomer, the constituent unit derived from the nonionic crosslinkable monomer, and the constituent unit derived from the anionic monomer to the respective monomers at the time of feeding for production is the same. That is, another embodiment is an additive for cement which contains a water-absorbent resin, wherein the water-absorbent resin has 50 mol% or more of a constituent unit derived from a nonionic non-crosslinkable monomer and 0.1 mol% or more of a constituent unit derived from a nonionic crosslinkable monomer, and the constituent unit derived from an anionic monomer is 20 mol% or less.

In a preferred embodiment of the present invention, the additive for cement contains a water-absorbent resin, wherein the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mass% or more of a nonionic crosslinkable monomer and 0.1 mass% or more of a nonionic crosslinkable monomer, and the content of an anionic monomer in the monomer mixture is 20 mass% or less.

(nonionic non-crosslinkable monomer)

The nonionic non-crosslinkable monomer is a main component of the monomer component constituting the water-absorbent resin. The nonionic non-crosslinkable monomer is a monomer having one unsaturated double bond in the monomer.

The nonionic non-crosslinkable monomer is preferably water-soluble because the effects of the present invention can be further exhibited. Hereinafter, the water-soluble nonionic non-crosslinkable monomer is also referred to as a water-soluble nonionic non-crosslinkable monomer. The term "water-soluble" in the water-soluble nonionic non-crosslinkable monomer means that 5g or more of the monomer is dissolved in 100g of water at 25 ℃. The water-soluble nonionic non-crosslinkable monomer is preferably dissolved in 100g of water at 25 ℃ in an amount of 10g or more, more preferably 50g or more, and still more preferably 100g or more.

The nonionic non-crosslinkable monomer is not particularly limited as long as it has one unsaturated double bond in the monomer. The nonionic, non-crosslinking monomers preferably do not include N-vinylamides ("N-vinylamides" in Japanese text: N- ビニルアシルアミド). Specific examples of the nonionic non-crosslinkable monomer include: (meth) acrylamide monomers such as (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide; n-vinyl lactam monomers such as N-vinyl pyrrolidone; hydroxy (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth) acrylate; unsaturated amines such as N- (2-dimethylaminoethyl) (meth) acrylamide, vinylpyridine, and vinylimidazole; acrylonitrile monomers such as acrylonitrile and methacrylonitrile; an unsaturated polyalkylene glycol alkenyl ether monomer represented by the following general formula (1);

[ solution 1]

(in the general formula (1), R¹、R²And R³Each independently represents a hydrogen atom or a methyl group; r⁴Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; r^aO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms; n represents R^aThe average addition mole number of oxyalkylene group represented by O, n is a number of 1 to 500; x is an integer of 0-2; y is 0 or 1. ) And the like. These substances may be used alone or in combination of 2 or more.

In the above general formula (1), R⁴Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include: an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), an alkenyl group having 1 to 30 carbon atoms, an alkynyl group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and the like. Among them, the hydrocarbon group is preferably an alkyl group, and more preferably an aliphatic alkyl group. In the point that the effects of the present invention can be further exhibited, R⁴Preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, still more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the general formula (1), n is a number of 1 to 500, but is preferably 10 to 300, more preferably 10 to 100. R^aO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably an oxyalkylene group having 2 to 4 carbon atoms. R^aThe addition system of O may be any of random addition, block addition, alternating addition, and the like. Need toIn order to secure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group contains an oxyethylene group as an essential component, more preferably 50 mol% or more of the whole oxyalkylene group is an oxyethylene group, still more preferably 90 mol% or more of the whole oxyalkylene group is an oxyethylene group, and particularly preferably 100 mol% of the whole oxyalkylene group is an oxyethylene group. The unsaturated polyalkylene glycol alkenyl ether monomer represented by the above general formula (1) can be produced by a conventionally known method.

Furthermore, since the nonionic non-crosslinkable monomer has excellent water-absorbing properties over a long period of time, it can be hydrolyzed by immersing it in an aqueous solution of pH12.9 at 25 ℃ for 24 hours. The nonionic non-crosslinkable monomer is hydrolyzed under a strong alkaline condition after 24 hours, and thus tends to have a characteristic that water absorption performance is exhibited after time (for example, after 2 hours). Here, the nonionic non-crosslinkable monomer was hydrolyzed when immersed in an aqueous solution of ph12.9 at 25 ℃ for 24 hours, which was confirmed by the results of measuring the aqueous solution using Liquid Chromatography (LC). Examples of the nonionic non-crosslinkable monomer to be subjected to such hydrolysis include: and hydroxy (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth) acrylate.

In addition, from the viewpoint of the initial water absorption inhibition performance, it is preferable that the nonionic non-crosslinkable monomer is not hydrolyzed when immersed in an aqueous solution of pH12.9 at 25 ℃ for 2 hours. Here, the term "not hydrolyzed" means that the ratio of hydrolysis (hydrolysis ratio) is 5% by mass or less. Since the nonionic non-crosslinkable monomer maintains its structure by not undergoing hydrolysis within 2 hours, water absorption hardly develops at the initial stage. Examples of such a nonionic non-crosslinkable monomer that is not hydrolyzed at the initial stage include acrylamide, N-hydroxymethyl (meth) acrylamide, and the like.

In addition, from the viewpoint of excellent water absorption performance over time, the nonionic non-crosslinkable monomer preferably contains at least 1 selected from the group consisting of a (meth) acrylamide-based monomer, a hydroxy (meth) acrylate, and an unsaturated polyalkylene glycol alkenyl ether-based monomer represented by the above general formula (1), more preferably contains a (meth) acrylamide-based monomer, still more preferably contains a (meth) acrylamide, and particularly preferably contains an acrylamide. Further, the nonionic non-crosslinkable monomer may be only (meth) acrylamide or only acrylamide. In another preferred embodiment, the nonionic non-crosslinkable monomer is a combination of a (meth) acrylamide monomer and an unsaturated polyalkylene glycol alkenyl ether monomer represented by the above general formula (1).

The content of the nonionic non-crosslinkable monomer in the monomer mixture is 50 mol% or more. When the content of the nonionic non-crosslinkable monomer is 50 mol% or more, the viscosity and fluidity of the cement composition at the initial stage are not easily changed even when the nonionic non-crosslinkable monomer is added. From the viewpoint of inhibiting the initial water absorption performance, the content of the nonionic non-crosslinkable monomer in the monomer mixture is preferably 75 mol% or more, 80 mol% or more, 85 mol% or more, 90 mol% or more, 93 mol% or more, 95 mol% or more, 97 mol% or more, 98 mol% or more, and 99 mol% or more in this order. From the viewpoint of ensuring the water absorbing performance, the upper limit of the content of the nonionic non-crosslinkable monomer in the monomer mixture is preferably 99.9 mol% or less, and more preferably 99.85 mol% or less. The content of each monomer in the monomer mixture was determined to be at the 2 nd position after the decimal point.

(nonionic crosslinking monomer)

The nonionic crosslinking monomer is a monomer having 2 or more polymerizable unsaturated groups. The water absorption performance is improved by forming a cross-linking structure (cross-linked body) by the non-ionic cross-linking monomer.

Since the effects of the present invention can be further exhibited, the nonionic crosslinkable monomer is preferably water-soluble. Hereinafter, the water-soluble nonionic crosslinking monomer is also referred to as a water-soluble nonionic crosslinking monomer. The term "water-soluble" in the water-soluble nonionic crosslinkable monomer means that 5g or more of the monomer is dissolved in 100g of water at 25 ℃. The water-soluble nonionic crosslinkable monomer is preferably dissolved in 100g of water at 25 ℃ in an amount of 10g or more, more preferably 50g or more, and still more preferably 100g or more.

The nonionic crosslinkable monomer is not particularly limited, but is preferably a compound having 2 or more polymerizable unsaturated groups, and examples thereof include: (meth) acrylamide monomers such as N, N' -methylenebis (meth) acrylamide; polyfunctional (meth) acrylates such as (poly) Ethylene glycol di (meth) acrylate (e.g., diethylene glycol diacrylate, (poly) propylene glycol di (meth) acrylate), trimethylene trimethanol tri (meth) acrylate, oxyethylene (Ethylene oxide, Japanese text: エチレンオキサイド) modified trimethylene trimethanol tri (meth) acrylate, and pentaerythritol hexa (meth) acrylate; allyl esters of cyanuric acid or isocyanuric acid such as triallyl cyanurate and triallyl isocyanurate; and the like. These can be used alone or in combination of 2 or more.

Among these, the nonionic crosslinkable monomer is a (meth) acrylamide-based monomer such as allyl ester of cyanuric acid or isocyanuric acid or polyfunctional (meth) acrylate, and the nonionic crosslinkable monomer is preferably a (meth) acrylamide-based monomer, and from the viewpoint of improving the long-term strength, the nonionic crosslinkable monomer preferably contains a (meth) acrylamide-based monomer, more preferably contains N, N '-methylenebis (meth) acrylamide, and still more preferably contains N, N' -methylenebisacrylamide. Further, the nonionic crosslinking monomer may be only a (meth) acrylamide monomer, only N, N '-methylenebis (meth) acrylamide, or only N, N' -methylenebisacrylamide.

The content of the nonionic crosslinking monomer in the monomer mixture is 0.1 mol% or more. The effect of the present invention is exhibited by the content of the nonionic crosslinking monomer being 0.1 mol% or more. In view of the fact that the cement composition at the initial stage of addition has a low viscosity and the effect of the present invention is superior in long-term strength, the content of the nonionic crosslinkable monomer in the monomer mixture is preferably in the order of 0.15 mol% or more, 0.2 mol% or more, and 0.5 mol% or more. The content of the nonionic crosslinkable monomer in the monomer mixture may be 0.8 mol% or more, or may be 1.0 mol% or more, from the viewpoint of low viscosity of the cement composition at the initial stage of addition. It is considered that by having a crosslinked structure with a high density, water held by the water-absorbent resin can be slowly released to the cement composition, and the long-term strength is improved. From the viewpoint of water absorption performance, the content of the nonionic crosslinkable monomer in the monomer mixture is preferably 8.0 mol% or less, more preferably 5.0 mol% or less, and still more preferably 3.0 mol% or less.

The nonionic crosslinkable monomer may be added in total to the aqueous nonionic crosslinkable monomer solution after preparation before the polymerization step, or may be added in part after the start of the polymerization.

(anionic monomer)

The anionic monomer refers to a monomer having an anionic functional group or a group of salts thereof in the monomer. The anionic functional group is a functional group in which a counter ion is dissociated into an anion (anionized).

Examples of the anionic functional group or a salt thereof include: sulfonic acid (salt) group, sulfuric acid (salt) group, phosphoric acid (salt) group, phosphonic acid (salt) group, carboxylic acid (salt) group (carboxyl group or salt thereof) and the like.

Examples of the anionic monomer include: (meth) acrylic acid, maleic acid (anhydride), itaconic acid, cinnamic acid, vinylsulfonic acid, allyltoluenesulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, methacrylsulfonic acid, 2-sulfoethylmethacrylic acid Na, anionic unsaturated monomers such as 2-hydroxy-3-allyloxypropane sulfonic acid, isoprene sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, 2- (meth) acryloyl ethane sulfonic acid, 2- (meth) acryloyl propane sulfonic acid, 2-hydroxyethyl (meth) acryloyl phosphate, phosphoric acid mono (2-hydroxyethyl) methacrylate, phosphoric acid mono (2-hydroxyethyl) acrylate, polyalkylene glycol mono (meth) acrylate acid phosphate, and salts thereof.

The content of the anionic monomer in the monomer mixture is 20 mol% or less. When the content of the anionic monomer in the monomer mixture exceeds 20 mol%, water absorption by the water-absorbent resin occurs at an initial stage, for example, 5 minutes after the water is added, and the viscosity of the cement composition rises sharply. From the viewpoint of ensuring initial fluidity and viscosity, the content of the anionic monomer in the monomer mixture is preferably less than 10 mol%, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, and most preferably 0 mol% (that is, no anionic monomer is contained).

In the present embodiment, a cationic monomer may be contained in addition to the nonionic monomer and the anionic monomer. The cationic monomer refers to a monomer having a cationic functional group or a group of a salt thereof in the monomer. The cationic functional group means a functional group in which a counter ion is dissociated into a cation (cationization).

Examples of the cationic monomer include: quaternized N-vinylimidazole, quaternized N-allylimidazole, quaternized 4-vinylpyridine, quaternized 1- [2- (acryloyloxy) ethyl ] -1H-imidazole, 1- [2- (methacryloyloxy) ethyl ] -1H-imidazole, and salts thereof.

In the present embodiment, the content of the cationic monomer in the monomer mixture is preferably 20 mol% or less, and is preferably less than 10 mol%, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol% or less, 1 mol% or less, and most preferably 0 mol% in order of preference (that is, the cationic monomer is not contained).

In a preferred embodiment of the present invention, the water-absorbent resin does not contain an ionic monomer (anionic monomer and cationic monomer), that is, the water-absorbent resin is obtained by polymerizing a nonionic non-crosslinkable monomer and a nonionic crosslinkable monomer.

(Process for production of Water-absorbent resin)

The method for producing the water-absorbent resin is not particularly limited, and the water-absorbent resin can be produced by a conventionally known method. Examples of the polymerization method for obtaining the water-absorbent resin include: spray polymerization, droplet polymerization ("droplet polymerization" in japanese text: droplet superposition), bulk polymerization, precipitation polymerization, aqueous solution polymerization, or reversed-phase suspension polymerization, and the like, and a production method using aqueous solution polymerization is exemplified here as an example.

(1) Process for producing aqueous solution of monomer mixture

This step is a step of dissolving each monomer constituting the polymer in water as a solvent to prepare an aqueous monomer mixture solution.

The monomers may be added together or sequentially. Here, the aqueous solution is a concept including an aqueous dispersion. The aqueous monomer mixture solution may contain, if necessary, components constituting additives for cement such as minor components (chelating agent, surfactant, dispersant, etc.).

The solvent of the "aqueous solution" in the aqueous monomer mixture solution is not limited to water in 100% by mass, and a water-soluble organic solvent (e.g., alcohol) may be used in combination in an amount of 0 to 30% by mass, preferably 0 to 5% by mass.

(2) Aqueous solution polymerization step

Aqueous solution polymerization is a method of polymerizing an aqueous monomer solution without using a dispersion solvent, and is disclosed in, for example, U.S. Pat. No. 4625001, No. 4873299, No. 4286082, No. 4973632, No. 4985518, No. 5124416, No. 5250640, No. 5264495, No. 5145906, No. 5380808, No. 0811636, No. 0955086, No. 0922717, and the like.

The concentration of the aqueous monomer solution during the polymerization is not particularly limited, but is preferably 20 mass% to the saturated concentration or less, more preferably 25 to 80 mass%, and still more preferably 30 to 70 mass%. When the concentration is 20% by mass or more, the decrease in productivity can be suppressed. Further, since the physical properties are deteriorated in the polymerization in the slurry (aqueous dispersion) of the monomer, it is preferable to carry out the polymerization at a saturated concentration or less.

In the polymerization step, a polymerization initiator is added to the aqueous monomer mixture solution obtained above.

The polymerization initiator to be used is appropriately determined depending on the polymerization system, and is not particularly limited, and examples thereof include: a photodecomposition type polymerization initiator, a thermal decomposition type polymerization initiator, a redox type polymerization initiator, and the like. These polymerization initiators are used to initiate polymerization.

Examples of the photodecomposition polymerization initiator include: benzoin derivatives, benzyl derivatives, acetophenone derivatives, benzophenone derivatives, azo compounds, and the like. Specifically, there are: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, alpha-methylbenzoin, alpha-phenylbenzoin, anthraquinone, methylanthraquinone, acetophenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylpropanone, benzyl diacetylacetophenone, benzophenone, p-chlorobenzophenone, 2-hydroxy-2-methylpropiophenone, diphenyl disulfide, tetramethylthiuram sulfide, alpha-chloromethyl naphthalene, anthracene, hexachlorobutadiene, pentachlorobutadiene, Michler's ketone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, benzyl dimethyl ketal, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, and the like. The photo-decomposition type polymerization initiator may be a commercially available product, and may be exemplified by Irgacure (registered trademark) 184 (hydroxycyclohexyl-phenyl ketone), Irgacure (registered trademark) 2959(1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one), and the like, which are tradenames of gasoline and gasoline.

Further, examples of the thermal decomposition type polymerization initiator include: persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; peroxides such as hydrogen peroxide, t-butyl peroxide, and methyl ethyl ketone peroxide; and azo compounds such as 2,2 '-azobis (2-amidinopropane) dihydrochloride and 2, 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride.

Further, examples of the redox polymerization initiator include a combination of the persulfate and the peroxide, and a reducing compound such as L-ascorbic acid or sodium hydrogen sulfite.

Further, the above-mentioned photodecomposition type polymerization initiator and thermal decomposition type polymerization initiator may be used in combination. Further, the polymerization initiator may be used alone or in combination with an active energy ray such as ultraviolet ray, electron beam, or γ ray.

The amount of the polymerization initiator used is preferably 0.0001 to 1 mol%, more preferably 0.0005 to 0.5 mol%, based on the monomer.

The polymerization step may be carried out under any of normal pressure, reduced pressure and increased pressure, but is preferably carried out under normal pressure (or a pressure in the vicinity thereof, usually. + -. 10 mmHg). The temperature at the start of the polymerization also varies depending on the type of the polymerization initiator used, but is preferably 15 to 130 ℃ and more preferably 20 to 120 ℃.

This gives a gel-like crosslinked polymer.

(3) Gel pulverization step

This step is an arbitrary step of obtaining a particulate hydrogel (hereinafter referred to as "particulate hydrogel") by gel-crushing a gel-like crosslinked polymer (hereinafter referred to as "hydrogel") obtained through the above-mentioned polymerization step and the like (particularly aqueous solution polymerization).

The gel mill that can be used is not particularly limited, and examples thereof include: a gel mill, a single-screw extruder, a twin-screw extruder, a chopper mixer, and the like, each of which is equipped with a plurality of rotating stirring blades, such as a batch-type or continuous double-arm kneader. Among them, a screw type extruder having a perforated plate at the tip is preferable, and examples thereof include those disclosed in Japanese patent laid-open No. 2000-063527.

(4) Drying step

This step is a step of drying the hydrogel obtained through the polymerization step and the like to obtain a dried polymer. In the case where the polymerization step is aqueous solution polymerization, the gel is pulverized (grain-sized) before and/or after drying of the hydrogel. The dried polymer (aggregate) obtained in the drying step may be directly supplied to the pulverizing step.

The drying method is not particularly limited, and various methods can be employed. Specifically, there may be mentioned: heating drying, hot air drying, reduced pressure drying, infrared ray drying, microwave drying, azeotropic dehydration drying using a hydrophobic organic solvent, high humidity drying using high temperature steam, etc., 1 or 2 of these methods may be used in combination. The drying temperature is preferably 100 to 300 ℃, and more preferably 120 to 250 ℃. The drying time is preferably 1 minute to 5 hours, for example, depending on the surface area and water content of the hydrogel, the type of the dryer, and the like.

(5) Grinding/classifying procedure

This step is a step of pulverizing and/or classifying the dried polymer obtained in the above-mentioned drying step, preferably to obtain a water-absorbent resin having a specific particle size. Further, the method is different from the method (3) in that the object to be pulverized is subjected to a drying step. The water-absorbent resin after the pulverization step may be referred to as a pulverized product.

The particle size can be controlled in the pulverization/classification step in the polymerization step, the gel pulverization step or the drying step, and particularly preferably in the classification step after drying.

[ other ingredients ]

The additive for cement comprises a water-absorbent resin as a main component. The main component is 80 mass% or more, preferably 90 mass% or more, more preferably 95 mass% or more, and most preferably 98 mass% or more (the upper limit is 100 mass%, that is, the additive for cement is composed only of the water-absorbent resin) of the additive for cement. The water-absorbent resin in the present invention also includes a water-absorbent resin obtained by subjecting the obtained polymer to any chemical modification (surface modification, etc.). The water-absorbent resin is preferably a water-absorbent resin composed only of a polymer obtained by polymerizing the monomer mixture.

The cement additive may contain 0 to 10 mass%, preferably 0.1 to 1 mass%, of each of a surfactant, an anti-coloring agent, a reducing agent and the like, in addition to the water-absorbent resin, for the purpose of stabilizing the water-absorbent resin and the like.

< admixture for cement >

The second embodiment of the present invention is an admixture for cement comprising the additive for cement and the cement dispersant of the first embodiment. By using both of them in combination, even in the case of adding the cement composition, the cement dispersibility can be maintained and the viscosity of the cement composition can be kept low even in the region where the amount of the cement dispersant added is small, and the long-term strength of the molded article can be improved.

As the cement dispersant, a conventionally known cement dispersant can be used. Examples of the cement dispersant include: polyalkyl aryl sulfonates such as naphthalenesulfonic acid-formaldehyde condensate; melamine formaldehyde resin sulfonates such as melamine sulfonic acid-formaldehyde condensates; aromatic sulfamates such as an aminoarylsulfonic acid-phenol-formaldehyde condensate; lignosulfonate salts such as lignosulfonate and modified lignosulfonate salts; various sulfonic acid dispersants having a sulfonic acid group in the molecule, such as polystyrene sulfonate; copolymers obtained from polyalkylene glycol mono (meth) acrylate monomers, (meth) acrylic monomers and monomers copolymerizable with these monomers, as described in Japanese patent publication No. 59-18338 and Japanese patent application laid-open No. 7-223852; various polycarboxylic acid dispersants having a (poly) oxyalkylene group and a carboxyl group in the molecule, such as copolymers obtained from unsaturated (poly) alkylene glycol ether monomers, maleic acid monomers or (meth) acrylic acid monomers as described in Japanese patent application laid-open Nos. H10-236858, 2001-220417, 2002-121055, 2002-121056 and 2018-111622; various phosphoric acid dispersants having a (poly) oxyalkylene group and a phosphoric acid group in the molecule, such as copolymers obtained from (alkoxy) polyalkylene glycol mono (meth) acrylate, a phosphoric acid monoester monomer and a phosphoric acid diester monomer as described in jp 2006-52381 a, and phosphoric acid dispersants described in jp 2008-517080 a. Among these, a polycarboxylic acid dispersant is preferably used as the cement dispersant in order to further exhibit the effects of the present invention. The number of the cement dispersants may be only 1, or may be 2 or more.

The content mass ratio of the cement dispersant to the cement additive in the admixture for cement is preferably 1: 0.1 to 10, more preferably 1: 0.5 to 5.

< Cement composition >

The third embodiment of the present invention is a cement composition containing the additive for cement of the first embodiment and cement.

Another embodiment of the present invention is a cement composition containing a water-absorbent resin and cement, wherein the water-absorbent resin is obtained by polymerizing a monomer mixture containing 50 mol% or more of a nonionic crosslinkable monomer and 0.1 mol% or more of a nonionic crosslinkable monomer, and the content of an anionic monomer in the monomer mixture is 20 mol% or less.

The content ratio of the cement additive (or the water-absorbent resin) in the cement composition can be any suitable content ratio according to the purpose. When the additive is used in mortar, concrete or the like using hydraulic cement, the content of the additive (or water-absorbent resin) for cement is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and still more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of cement. By setting the content ratio as described above, various satisfactory effects such as low viscosity, high fluidity, and increase in strength are produced.

The cement composition preferably contains water. The cement composition preferably contains aggregate.

As the cement, any appropriate cement can be used. Examples of such cement include: portland cement (ordinary, early strength, super early strength, moderate heat, sulfate resistance, and low alkali forms thereof), various mixed cements (blast furnace cement, silica cement, fly ash cement), white portland cement, alumina cement, quick-hardening cement (1 clinker quick-hardening cement (japanese script: クリンカー quick-hardening セメント), 2 clinker quick-hardening cement, magnesium phosphate cement), grouting cement (セメント for グラウト), oil well cement, low-heat bath cement (low-heat blast furnace cement, fly ash mixed low-heat blast furnace cement, belite high-content cement), super-high strength cement, cement-based setting materials, ecological cement (cement produced from at least one of municipal refuse incineration ash and sewer incineration ash) and the like. Further, fine powders such as blast furnace slag, fly ash, cinder ash, cement clinker ash, rice hull ash (ハスクアッシュ), silica powder, limestone powder, and gypsum may be added to the cement composition. The cement contained in the cement composition of the present invention may be only 1 type or 2 or more types.

In the cement composition, as it is per 1m³The unit water amount, the amount of cement used, and the water/cement ratio of (A) can be set to any appropriate values. Such a value is preferably 100kg/m per unit water amount³～185kg/m³The amount of cement used was 250kg/m³～800kg/m³The water/cement ratio (mass ratio) is 0.1 to 0.7, and the unit water amount is preferably 120kg/m³～180kg/m³The amount of cement used was 270kg/m³～800kg/m³The water/cement ratio (mass ratio) is 0.12-0.65.

As the aggregate, any suitable aggregate such as a fine aggregate (sand, etc.) and a coarse aggregate (crushed stone, etc.) can be used. Examples of such aggregate include: sand (land sand, etc.), broken stone, water-granulated slag and recycled aggregate. Further, as such aggregate, there can be mentioned: refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium-magnesium and magnesium oxide.

The cement composition preferably contains a cement dispersant. That is, a preferred embodiment of the present invention is a cement composition containing the additive for cement, and cement dispersant of the first embodiment. The cement dispersant is the same as the cement dispersant described in the section of the second embodiment.

The content mass ratio of the cement dispersant to the cement additive in the cement composition is preferably 1: 0.1 to 10, more preferably 1: 0.5 to 5. The content of the cement dispersant in the cement composition may be any suitable content depending on the purpose, and is, for example, 0.01 to 10 parts by mass per 100 parts by mass of cement.

The cement composition may contain any other suitable cement additive within a range not impairing the effects of the present invention. Examples of such other cement additives include other cement additives exemplified in the following (1) to (12). (1) Water-soluble high molecular substance: nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, and carboxymethyl cellulose; polysaccharides produced by microbial fermentation, such as yeast glucan, xanthan gum, and β -1,3 glucan; polyacrylamide, and the like. (2) High-molecular emulsion: copolymers of various vinyl monomers such as alkyl (meth) acrylates, and the like. (3) Curing retarder: hydroxycarboxylic acids such as gluconic acid, glucoheptonic acid, arabinonic acid, malic acid, and citric acid, and salts thereof; monosaccharides such as glucose, fructose, galactose, mannose, xylose, arabinose, ribose, and isomerized sugar; disaccharides such as maltose, sucrose, and lactose; trisaccharides such as raffinose; saccharides or sugar alcohols such as erythritol oligosaccharides including dextrin, xylitol, D-arabitol, L-arabitol, ribitol, heptatol, mannoheptitol, sorbitol, mannitol, galactitol, D-threitol, L-threitol, D-iditol, D-glycidol, and D-erythritol-D-galactitol-octitol (D- エリトロー D- ガラクト - オクチトール); polyhydric alcohols such as glycerin; phosphonic acids such as aminotri (methylenephosphonic acid) and derivatives thereof. (4) Early strength agent/accelerator: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, and calcium iodide; chlorides such as iron chloride and magnesium chloride; a sulfate salt; potassium hydroxide; sodium hydroxide; a carbonate salt; a thiosulfate salt; formic acid and formate such as calcium formate; an alkanolamine; alumina cement; calcium aluminate (カルシウムアルミネートシリケート), and the like. (5) Oxyalkylene-based defoaming agent: polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; (poly) oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; polyoxyalkylene alkyl (aryl) ether sulfate salts; polyoxyalkylene alkyl phosphates; polyoxyalkylene alkylamine such as amine of fatty acid (such as 1-20 mol addition of oxypropylene and 1-20 mol addition of oxyethylene) obtained by adding polyoxypropylene polyoxyethylene laurylamine (such as 1-20 mol addition of oxypropylene and 1-20 mol addition of oxyethylene) and Alkylene oxide (such as 1-20 mol addition of oxyethylene and 1-20 mol addition of oxyethylene) to cured tallow; polyoxyalkylene amides, and the like. (6) Antifoaming agents other than oxyalkylene group: mineral oils, fatty acids, fatty acid esters, alcohols, amides, phosphates, metallic soaps, silicones, and the like. (7) AE agent: resin soaps, saturated or unsaturated fatty acids, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzenesulfonic acid), alkane sulfonates, polyoxyethylene alkyl (phenyl) ethers, polyoxyethylene alkyl (phenyl) ether sulfates or salts thereof, polyoxyethylene alkyl (phenyl) ether phosphates or salts thereof, proteinaceous materials, alkenyl sulfosuccinic acids, α -olefin sulfonates, and the like. (8) Other surfactants: various anionic surfactants; various cationic surfactants such as alkyltrimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants, and the like. (9) Water-proofing agent: fatty acids (salts), fatty acid esters, oils and fats, silicone, paraffin, asphalt, wax, and the like. (10) Antirust agent: nitrites, phosphates, zinc oxide, and the like. (11) Chap reducing agent: polyoxyalkyl ethers, and the like. (12) An intumescent material; calcium alum stones, coal, and the like.

Other known cement additives include: a cement wetting agent, a thickener, a separation reducing agent, a coagulant, a drying shrinkage reducing agent, a strength enhancer, a self-leveling agent, a rust preventive, a coloring agent, a mildewproofing agent, and the like. These known cement additives (materials) may be only 1 type or 2 or more types. In addition, other cement additives may be added to the cement composition in an appropriate amount in consideration of the purpose of addition.

The cement composition is effective for ready-mixed concrete, concrete for concrete 2-time products, concrete for centrifugal molding, vibration-dense practical concrete, steam-cured concrete, shotcrete, and the like. The cement composition is also effective for mortar or concrete requiring high fluidity, such as medium-flow concrete (concrete having a slump value of 22 to 25 cm), high-flow concrete (concrete having a slump value of 25cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, and self-leveling material.

The cement composition may be prepared by mixing the constituent components by any suitable method. Examples thereof include a method of kneading the components in a mixer.

< aggregate composition >

A fourth embodiment of the present invention is an aggregate composition containing the additive for cement of the first embodiment and an aggregate. When both are used in combination, the uniformity becomes good when the cement composition is added. As the aggregate, the aggregate described in the column of the cement composition of the third embodiment can be used.

The mass ratio of the cement additive to the aggregate in the aggregate composition may be any appropriate content depending on the purpose. The content of the additive for cement (or water-absorbent resin) is preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass, based on 100 parts by mass of the aggregate.

< shaped body >

A fifth embodiment of the present invention is a molded article obtained by molding a cement composition.

The formation of the molded article is not particularly limited, and can be carried out by a conventionally known method. Examples of the molding method include: a method in which a cement composition is poured into a mold frame, each mold frame is cured, and thereafter, the mold is removed; and a method of curing a molded article released from a mold after pouring the cement composition into the mold.

The method of curing is not particularly limited, and may be any of water curing, sealing curing, and air curing. Alternatively, curing may be performed by applying a curing agent.

The molded article of the fifth embodiment can be used for various applications because it can withstand long-term use. Specifically, examples thereof include: buildings such as buildings; concrete structures such as columns, piles, side ditches, and the like.

< method for improving strength of molded article >

A sixth embodiment of the present invention is a method for improving the strength of a molded article obtained by molding a cement composition containing cement, including the step of including the additive for cement of the first embodiment in the cement composition.

The strength of the molded article may be more than 100% of the strength of the molded article before the addition of the cement additive, and is preferably 103% or more, more preferably 105% or more, and still more preferably 109% or more. The strength of the molded article to which the cement additive was added was measured by sealing and curing for 27 days by the method described in the following examples.

Examples

The effects of the present invention will be described with reference to the following examples and comparative examples. In the examples, "part(s)" or "%" may be used, and unless otherwise specified, "part(s) by mass" or "% by mass" is used. Unless otherwise specified, each operation was carried out at room temperature (25 ℃) and normal pressure.

Production example 1

A1000 ml cylindrical separable flask was charged with 29.9g of acrylamide, 0.0974g of N, N-methylenebisacrylamide, and 45.6g of water, and the mixture was uniformly dissolved. In the monomer mixture containing acrylamide and N, N-methylenebisacrylamide, the molar ratio was 99.85 mol% for acrylamide and 0.15 mol% for N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 12.53g of a 1% aqueous solution of sodium persulfate and 12.01g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 2

59.34g of acrylamide, 0.647g of N, N-methylenebisacrylamide, and 191.51g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. In the monomer mixture containing acrylamide and N, N-methylenebisacrylamide, the molar ratio was 99.49 mol% for acrylamide and 0.51 mol% for N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, 24.89g of a 1% aqueous solution of sodium persulfate and 23.86g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel polymer was finely divided by a cutter, then dried with hot air at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which had passed through the sieves having meshes of 500 μm and remained on the sieves having meshes of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 3

58.73g of acrylamide, 1.276g of N, N-methylenebisacrylamide, and 191.96g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. In the monomer mixture composed of acrylamide and N, N-methylenebisacrylamide, the molar ratio of acrylamide was 99.00 mol% and the molar ratio of N, N-methylenebisacrylamide was 1.00 mol%. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.66g of a 1% aqueous solution of sodium persulfate and 23.64g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel polymer was finely divided by a cutter, then dried with hot air at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which had passed through the sieves having meshes of 500 μm and remained on the sieves having meshes of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 4

Into a 1000ml cylindrical separable flask were charged 33.53g of acrylamide, 25.43g of hydroxyethyl methacrylate, 1.039g of N, N-methylenebisacrylamide and 200.55g of water, and the mixture was uniformly dissolved. In the monomer mixture containing acrylamide, hydroxyethyl methacrylate, and N, N-methylene bisacrylamide, acrylamide was 70.00 mol%, hydroxyethyl methacrylate was 29.00 mol%, and N, N-methylene bisacrylamide was 1.00 mol%. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 20.05g of a 1% aqueous solution of sodium persulfate and 19.4g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 5

Into a 1000ml cylindrical separable flask were charged 42.4g of acrylamide, 16.45g of hydroxyethyl acrylate, 1.15g of N, N-methylenebisacrylamide, and 196.34g of water, and the mixture was uniformly dissolved. In the monomer mixture containing acrylamide, hydroxyethyl acrylate, and N, N-methylenebisacrylamide, 80.00 mol% of acrylamide, 19.00 mol% of hydroxyethyl methacrylate, and 1.00 mol% of N, N-methylenebisacrylamide were used. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 6

58.73g of acrylamide, 1.276g of N, N-methylenebisacrylamide, and 191.96g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. In the monomer mixture containing acrylamide and N, N-methylenebisacrylamide, the molar ratio was 99.00 mol% for acrylamide and 1.00 mol% for N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.66g of a 1% aqueous solution of sodium persulfate and 23.64g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having mesh openings of 710 μm and 500 μm, and the water-absorbent resin was collected as a powder which passed through a sieve having mesh openings of 710 μm and remained on a sieve having mesh openings of 500 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 7

58.73g of acrylamide, 1.276g of N, N-methylenebisacrylamide, and 191.96g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. In the monomer mixture containing acrylamide and N, N-methylenebisacrylamide, the molar ratio was 99.00 mol% for acrylamide and 1.00 mol% for N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.66g of a 1% aqueous solution of sodium persulfate and 23.64g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having mesh openings of 250 μm and 125 μm, and a powdery water-absorbent resin was collected which passed through a sieve having mesh openings of 250 μm and remained on a sieve having mesh openings of 125 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 8

Into a 1000ml cylindrical separable flask were charged 47.92g of acrylamide, 10.8g of acrylic acid, 1.283g of N, N-methylenebisacrylamide, and 191.27g of water, and the mixture was uniformly dissolved. Here, the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide included 18.00 mol% of acrylic acid, 81.00 mol% of acrylamide and 1.00 mol% of N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.77g of a 1% aqueous solution of sodium persulfate and 23.96g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 9

53.86g of acrylamide, 4.96g of acrylic acid, 1.18g of N, N-methylenebisacrylamide, and 191.2g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. Here, the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide included 9.00 mol% of acrylic acid, 90.00 mol% of acrylamide, and 1.00 mol% of N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.81g of a 1% aqueous solution of sodium persulfate and 24g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 10

Into a 1000ml cylindrical separable flask were charged 56.31g of acrylamide, 2.4g of acrylic acid, 1.286g of N, N-methylenebisacrylamide, and 191.18g of water, and the mixture was uniformly dissolved. In the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide, acrylic acid was 4.00 mol%, acrylamide was 95.00 mol%, and N, N-methylenebisacrylamide was 1.00 mol%. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.82g of a 1% aqueous solution of sodium persulfate and 24.01g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 11

A1000 ml cylindrical separable flask was charged with 60.87g of acrylamide, 2.13g of triallyl isocyanurate, and 186.37g of water, and the mixture was uniformly dissolved. In the monomer mixture containing acrylamide and triallyl isocyanurate, the molar ratio was 99.00 mol% for acrylamide and 1.00 mol% for triallyl isocyanurate. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, 26g of a 1% aqueous solution of sodium persulfate and 24.92g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Production example 12

Into a 1000ml cylindrical separable flask were charged 3.8g of acrylamide, 6.21g of hydroxyethyl acrylate, 51.99g of a substance obtained by adding ethylene oxide to the hydroxyl group of 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of ethylene oxide: 50), 1.0g of triallyl isocyanurate, and 229.02g of water, and these substances were uniformly dissolved. In the monomer mixture containing acrylamide, hydroxyethyl acrylate, a substance obtained by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and triallyl isocyanurate, the amounts were 40 mol% of acrylamide, 40 mol% of hydroxyethyl acrylate, 17 mol% of a substance obtained by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and 3 mol% of triallyl isocyanurate. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 4.096g of a 1% aqueous solution of sodium persulfate and 3.927g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. The powdery water-absorbent resin is used as an additive for cement.

Production example 13

Into a 1000ml cylindrical separable flask were charged 1.34g of acrylamide, 61.31g of a substance obtained by adding oxyethylene to the hydroxyl group of 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), 0.35g of triallyl isocyanurate, and 234.19g of water, and these substances were uniformly dissolved. Here, in the monomer mixture containing acrylamide, a substance formed by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and triallyl isocyanurate, the amount was 40 mol% of acrylamide, a substance formed by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and triallyl isocyanurate was 3 mol%. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 1.44g of a 1% aqueous solution of sodium persulfate and 1.381g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. The powdery water-absorbent resin is used as an additive for cement.

Production example 14

Into a 1000ml cylindrical separable flask were charged 3.83g of acrylamide, 6.25g of hydroxyethyl acrylate, 52.38g of a substance obtained by adding oxyethylene to the hydroxyl group of 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), 0.54g of diethylene glycol diacrylate and 228.96g of water, and these were uniformly dissolved. In the monomer mixture including acrylamide, hydroxyethyl acrylate, a substance obtained by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and diethylene glycol diacrylate, the monomer mixture included 40 mol% of acrylamide, 40 mol% of hydroxyethyl acrylate, 17 mol% of a substance obtained by adding a hydroxyl group of oxyethylene to 3-methyl-3-buten-1-ol (prenol) (the average molar number of addition of oxyethylene is 50), and 3 mol% of diethylene glycol diacrylate. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 4.126g of a 1% aqueous solution of sodium persulfate and 3.956g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. The powdery water-absorbent resin is used as an additive for cement.

Production example 15

In a 1000ml cylindrical separable flask, 52.88g of hydroxyethyl acrylate, 9.44g of sodium 2-acrylamido-2-methylpropanesulfonate, 0.68g of diethylene glycol diacrylate and 207.37g of water were placed and dissolved uniformly. Here, in the monomer mixture including hydroxyethyl acrylate, sodium 2-acrylamido-2-methylpropanesulfonate, and diethylene glycol diacrylate, 90 mol% of hydroxyethyl acrylate, 9 mol% of sodium 2-acrylamido-2-methylpropanesulfonate, and 1 mol% of diethylene glycol diacrylate were included. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 15.21g of a 1% aqueous solution of sodium persulfate and 14.58g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat generation was carried out, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. The powdery water-absorbent resin is used as an additive for cement.

Comparative production example 1

41.06g of acrylamide, 18.74g of acrylic acid, 0.19g of N, N-methylenebisacrylamide and 91.20g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. Here, the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide included 31.00 mol%, 68.85 mol%, and 0.15 mol% of acrylic acid, acrylamide and N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.80g of a 2% aqueous solution of sodium persulfate and 23.99g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel polymer was finely divided by a cutter, then dried with hot air at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which had passed through the sieves having meshes of 500 μm and remained on the sieves having meshes of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

Comparative production example 2

41.06g of acrylamide, 18.74g of acrylic acid, 0.19g of N, N-methylenebisacrylamide and 91.20g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. Here, the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide included 31.00 mol%, 68.85 mol%, and 0.15 mol% of acrylic acid, acrylamide and N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.80g of a 2% aqueous solution of sodium persulfate and 23.99g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel polymer was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and then pulverized by a mixer and classified. The classification was carried out in the same manner as in [117] to [119] of Japanese patent laid-open publication No. 2015-048386 to obtain a powdery water-absorbent resin. The powdery water-absorbent resin is used as an additive for cement. The average particle diameter of the powdery water-absorbent resin was 50 μm. The average particle diameters of comparative production examples 2 and 3 were measured as follows: a laser diffraction particle size distribution apparatus LA-920 (manufactured by HORIBA Co., Ltd.) was used, and the distribution was set as follows: standard, particle size basis: volume, graph mode: after the bar chart, methanol was put into the sample bath, and air was evacuated and the optical axis was adjusted. Subsequently, the sample was placed in a sample bath, ultrasonic waves were applied for 2 minutes simultaneously with the sample being put in, and the sample concentration was adjusted so that the transmittance became 81 to 88%. For the measurement, after the sample concentration was adjusted, the ultrasonic treatment was performed again for 2 minutes.

Comparative production example 3

41.06g of acrylamide, 18.74g of acrylic acid, 0.19g of N, N-methylenebisacrylamide and 91.20g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. Here, the monomer mixture containing acrylic acid, acrylamide and N, N-methylenebisacrylamide included 31.00 mol%, 68.85 mol%, and 0.15 mol% of acrylic acid, acrylamide and N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.80g of a 2% aqueous solution of sodium persulfate and 23.99g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel polymer was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and then pulverized by a mixer and classified. The classification was carried out in the same manner as in [123] to [125] of Japanese patent laid-open publication No. 2015-048386 to obtain a powdery water-absorbent resin. The powdery water-absorbent resin is used as an additive for cement. The average particle diameter of the powdery water-absorbent resin was 15 μm.

Comparative production example 4

59.99g of acrylamide, 0.013g of N, N-methylenebisacrylamide, and 191.07g of water were put into a 1000ml cylindrical separable flask and uniformly dissolved. In the monomer mixture containing acrylamide and N, N-methylenebisacrylamide, the molar ratio was 99.99 mol% for acrylamide and 0.01 mol% for N, N-methylenebisacrylamide. After the flask was purged with nitrogen, the mixture was heated to 45 ℃ on a hot water bath, and 24.87g of a 1% aqueous solution of sodium persulfate and 24.06g of a 0.1% aqueous solution of L-ascorbic acid were added thereto, and the polymerization was carried out while stopping the stirring. After the polymerization started, heat was generated, and the temperature was increased to 80 ℃ after 10 minutes. The bath temperature was raised to 80 ℃ at the time when the rise of the liquid temperature was stopped, and aging was carried out for 30 minutes. The obtained gel-like polymer (hydrogel) was finely divided by a cutter, then hot-air dried at 130 ℃ for 3 hours, and after grinding by a mixer, it was sieved by JIS standard sieves having meshes of 500 μm and 250 μm, and a powdery water-absorbent resin was collected which passed through a sieve having a mesh of 500 μm and remained on a sieve having a mesh of 250 μm. 90 mass% or more of the powdery water-absorbent resin is in the range of 45 to 850 μm. Further, 90 mass% or more of the powdery water-absorbent resin is in the range of 100 to 850. mu.m. The powdery water-absorbent resin is used as an additive for cement.

[ Water absorption test method ]

Mixing CaSO₄·2H₂O 1.72g、Na₂SO₄ 6.96g、K₂SO₄4.76g, KOH 7.12g, and deionized water 979.4g were mixed to prepare a solution (pH12.9) for a water absorption test.

About 0.2g (mass W1(g)) of the powdery water-absorbent resin was weighed accurately, and the weighed powdery water-absorbent resin was put into a tea bag made of a nonwoven fabric of 4 cm. times.5 cm and sealed by heat-sealing. The tea bag was placed in a screw tube made of glass and having a predetermined volume of 50mL, and immersed in 50mL of a solution for a water absorption test at room temperature (25 ℃ C.) and under normal pressure for a predetermined period of time (5 minutes, 2 hours, 28 days). Then, the end of the tea bag was nipped by tweezers and the tea bag was taken out, and one side of the tea bag was left standing for 5 seconds while being placed on KIMTOWEL (manufactured by Nippon paper Crecia Co., Ltd.) for downloading. Subsequently, the opposite side was left standing for 5 seconds for the next download on a KIMTOWEL, and water control was performed, and then the quality of the tea bag was measured (W2 (g)). The same procedure was carried out without using the water-absorbent resin, and the mass of the tea bag (W3(g)) was determined as a blank. The water absorption capacity calculated according to the following formula was defined as liquid absorption capacity.

[ number 1]

Water absorption multiple (g/g) ═ W2(g) -W3(g))/W1(g)

The water absorption capacity of each powdery water-absorbent resin is shown in table 1 below.

[ Table 1]

From the above results, it is known that: the powdery water-absorbent resins of production examples 1 to 15 had a water absorption capacity of 20g/g or less after 5 minutes had elapsed, a water absorption capacity of less than 20g/g even after 2 hours had elapsed, and a high water absorption capacity of 29g/g or more after 28 days had elapsed. On the other hand, the powdery water-absorbent resins of comparative production examples 1 to 3 had a water absorption capacity of more than 20g/g after 5 minutes had elapsed. The powdery water-absorbent resin of comparative production example 4 was 20g/g or less after 5 minutes had passed, but it exceeded 20g/g after 2 hours had passed. From the results, it is found that: the powdery water-absorbent resins of production examples 1 to 15 exhibited high water absorption performance with time, while the water absorption performance was not so high at the initial stage of water addition (up to about 2 hours).

The water absorption capacity of the powdery water-absorbent resin after being immersed for 5 minutes by the above-mentioned water absorption test method is preferably 20g/g or less, more preferably 15g/g or less, still more preferably 13g/g or less, yet more preferably 12g/g or less, particularly preferably 11g/g or less, and most preferably 10g/g or less.

Production example a: production of Cement dispersant

80.0 parts of ion-exchanged water was charged into a glass reaction vessel equipped with a diemol cooling tube, a stirring blade with teflon (registered trademark), a stirrer sealed by stirring, a nitrogen introduction tube, and a temperature sensor, and heated to 70 ℃ while introducing nitrogen gas at 200 mL/min under stirring at 250 rpm. Subsequently, a mixed solution of 133.4 parts of methoxypolyethylene glycol monomethacrylate (average molar number of addition of oxyethylene: 9), 26.6 parts of methacrylic acid, 1.53 parts of mercaptopropionic acid and 106.7 parts of ion-exchanged water was added dropwise over 4 hours, and at the same time, a mixed solution of 1.19 parts of ammonium persulfate and 50.6 parts of ion-exchanged water was added dropwise over 5 hours. After the completion of the dropwise addition, the reaction mixture was kept at 70 ℃ for 1 hour to complete the polymerization reaction. Then, the mixture was neutralized with an aqueous sodium hydroxide solution to obtain an aqueous polycarboxylic acid copolymer solution (solid content: about 46.0 mass%) containing a polymer as a cement dispersant.

Production example B: production of Cement dispersant

Into a glass reaction vessel equipped with a diemol cooling tube, a stirring blade equipped with teflon (registered trademark), a stirrer sealed by stirring, a nitrogen introduction tube, and a temperature sensor, 198.2 parts of a substance (hereinafter referred to as IPN-50) (80% aqueous solution) obtained by adding oxyethylene to the hydroxyl group of 3-methyl-3-buten-1-ol (isopentenol) (the average molar number of addition of oxyethylene is 50), 0.32 parts of acrylic acid, 12.47 parts of hydrogen peroxide water (2% aqueous solution), and 44.75 parts of ion-exchanged water were charged, and while stirring at 250rpm, nitrogen was introduced at 200 mL/min, the vessel was heated to 58 ℃. Subsequently, a mixed solution containing 27.12 parts of acrylic acid and 108.5 parts of ion-exchanged water was added dropwise over 3 hours, and at the same time, a mixed solution containing 0.74 parts of L-ascorbic acid, 1.61 parts of 3-mercaptopropionic acid and 86.31 parts of ion-exchanged water was added dropwise over 3 hours and 30 minutes. After the completion of the dropwise addition, the reaction mixture was kept at 58 ℃ for 1 hour to complete the polymerization reaction. Then, the mixture was neutralized with an aqueous sodium hydroxide solution to obtain an aqueous polycarboxylic acid copolymer solution (solid content: about 48.0 mass%) containing a polymer as a cement dispersant.

Production example C: production of Cement dispersant

An aqueous solution of a polycarboxylic acid-based copolymer containing a polymer as a cement dispersant (about 40 mass% as a solid content) was obtained according to the production method of production example C-1 of Japanese patent application laid-open No. 2018-111622.

Production example D: production of Cement dispersant

An aqueous solution of a polycarboxylic acid-based copolymer containing a polymer as a cement dispersant (about 40% by mass as a solid content) was obtained according to the production method of production example C-3 of Japanese patent application laid-open No. 2018-111622.

Production example E: production of Cement dispersant

An aqueous solution of a polycarboxylic acid-based copolymer containing a polymer as a cement dispersant (about 40% by mass as a solid content) was obtained according to the production method of production example C-4 of Japanese patent application laid-open No. 2018-111622.

Production example F: preparation of Cement dispersant

MIGATY 150 (a formaldehyde condensate of naphthalene sulfonate, manufactured by Kao corporation, solid content: about 40% by mass) was used as a dispersant.

Production example G: preparation of Cement dispersant

MasterPozzolithNo.8 (lignin sulfonic acid compound, manufactured by BASF Japan, solid content: about 100 mass%) was used as a dispersant.

Production example H: production of Cement dispersant

An aqueous solution of a phosphoric acid-based dispersant containing a condensate of polyethylene glycol (average molar number of addition of oxyethylene: 20 mol) monophenyl ether and phenoxyethanol phosphate having a ratio of the monophenyl ether to the phenoxyethanol phosphate of 30/70 (mol%) and a weight average molecular weight (Mw) of 25000 was obtained by condensation reaction with formaldehyde of polyethylene glycol (average molar number of addition of oxyethylene: 20 mol) according to the method described in Japanese patent application laid-open No. 2008-517080.

[ evaluation method 1: mortar test and Strength test method

A mechanical stirring kneader, a spoon, a flow test stand, a flow cone and a protrusion bar were used in accordance with JIS-R5201-1997. At this time, unless otherwise specified, mortar tests were carried out in accordance with JIS-R5201-1997.

The mortar (cement composition) was composed of 587g of ordinary portland cement manufactured by pacific cement corporation (excluding the amount of the water-absorbent resin to be added described below), 1350g of standard sand for cement strength test based on JIS-R5201-1997, 264.1g of ion-exchanged water containing the copolymer aqueous solutions (cement dispersants) obtained in production examples A to H and an antifoaming agent (the copolymer solid content was 0.11 to 0.31 parts by mass per 100 parts by mass of cement, Table 2 below), and a powdery water-absorbent resin. The powdery water-absorbent resin was previously added in an amount of 0.3 parts by mass (0.1 part by mass in examples 12 and 13) to 100 parts by mass of cement, and mixed with the cement. The antifoaming agent is added to the mortar composition so as to avoid the influence of air bubbles on the dispersibility of the mortar composition, and the amount of air is 4.0% or less. Specifically, the oxyalkylene-based defoaming agent was used in an amount of 0.1% relative to the copolymer. When the air amount of the mortar is more than 4.0%, the amount of the antifoaming agent is adjusted so that the air amount is 4.0% or less.

Mortar was prepared at room temperature (20. + -. 2 ℃ C.) for 4 minutes and 30 seconds using a Hobart type mortar mixer (model N-50, manufactured by Hobart corporation). Specifically, a predetermined amount of cement and a predetermined amount of powdery water-absorbent resin were put into a stirring bowl, and the mixer was set and started at a low speed. The impeller was started, and water containing predetermined amounts of the cement dispersant and the defoaming agent was added 15 seconds after 15 seconds. Thereafter, sand was added, and after kneading at a low speed for 30 seconds, the mixture was set at a high speed, and then kneading was continued for 30 seconds. The mixing bowl was removed from the mixer, the mixing was stopped for 120 seconds, and then the mixing bowl was attached to the mixer again, and after 60 seconds of high-speed mixing (after 4 minutes and 30 seconds from the start of starting at low speed), the mixture was left and right stirred 10 times with a spoon. The mixed slurry was divided into 2 layers and loaded into a flow cone placed on a flow test bench. Each layer was pierced 15 times over the entire surface so that the tip of the protruding rod entered about 1/2 times of the depth of the layer, and finally the insufficient component was replenished to flatten the surface, and the flow cone was vertically lifted 6 minutes after the start of the layer at low speed, and then the diameter of the slurry spread in the test bed was measured in the 2-direction, and the average value was set as the flow value.

For the measurement of the amount of mortar air, mortar was charged into a 500ml measuring cylinder, the weight and the volume were measured, and the difference in volume between the measured volume and the amount of mortar air charged at the weight was calculated as the amount of air.

After the flow value and the air amount were measured, mortar or concrete was poured into a mold to prepare a sample for a compressive strength test, and the compressive strength after 28 days was measured under the following conditions.

Preparing a test body: 50mm x 100mm

The test body was maintained for 1(28 days, sealed): after 24 hours of curing at about 20 ℃ and 60% humidity in constant temperature and humidity air, the test piece was demolded from the mold frame, and the test piece was wrapped with a polyethylene film (Japanese text: ポリフィルム for polyethylene film) so that the exchange of water between the mortar surface and the outside could not be performed, and then placed in a polyethylene bag (Japanese text: ポリ for polyethylene bag) and sealed, and sealed and cured for 27 days.

The test body was maintained for 2 days (28 days in air): after curing at about 20 ℃ and 60% humidity in air for 24 hours, the specimen was demolded from the mold frame, and the specimen was left to stand in the same environment and cured in air for 27 days.

Polishing a test body: surface polishing of test body (use polishing finishing machine of test body)

And (3) measuring the compressive strength: automatic compression strength tester (Qianchuan manufacturing institute)

[ evaluation method 2: funnel flow-down test method

As evaluation of piping passability in pumping, a funnel flow test of mortar was performed. The mortar was judged to have good piping passability without blocking in the middle and flowing down in a short time. The specific method of the funnel flow-down test is as follows.

A rubber stopper was attached to the lower end of a J14 funnel (upper end inner diameter 70mm, lower end inner diameter 14mm, height 392mm) specified in JSCE-F541 as standard of the society of civil engineering, and the rubber stopper was supported vertically by a stand. Next, an electronic scale for measuring the amount of the discharged slurry was installed below the lower end of the J14 hopper.

The resulting slurry was poured onto a J14 funnel, which was flattened. Next, the rubber stopper was removed to discharge mortar, and the time from the start of discharging mortar to 1200g of mortar was measured by a stopwatch and used as the funnel flow time.

The results of the examples and comparative examples are shown in table 2 below. The% in the column of 28-day strength is the% of each strength when the value of the same cement dispersant without the cement additive is 100%. Specifically, examples 1 to 13 and comparative examples 9 and 17 are the respective strengths when comparative example 1 is set to 100%, examples 14 and 10 are the respective strengths when comparative example 2 is set to 100%, examples 15 and 11 are the respective strengths when comparative example 3 is set to 100%, examples 16 and 12 are the respective strengths when comparative example 4 is set to 100%, examples 17 and 13 are the respective strengths when comparative example 5 is set to 100%, examples 18 and 14 are the respective strengths when comparative example 6 is set to 100%, examples 19 and 15 are the respective strengths when comparative example 7 is set to 100%, and examples 20 and 16 are the respective strengths when comparative example 8 is set to 100%.

[ Table 2-1]

[ tables 2-2]

[ tables 2 to 3]

From the above results, it is known that: the cement compositions using the cement additives of the examples had equivalent fluidity values to those of comparative examples 1 to 8 in which no cement additive was added. In addition, among the cement compositions having the same flow value (fluidity), the cement compositions using the cement additives of the examples had a smaller amount of cement dispersant than the cement compositions using the cement additives of comparative examples 9 to 17. Further, the cement compositions using the cement additives of the examples showed low viscosity and excellent pump transportability, because the flow-down time was short. The cement compositions using the cement additives of the examples were improved in sealing strength and curing strength in air over 28 days, as compared with those of comparative examples 1 to 8 in which no cement additive was added.

The sealing and curing conditions and the air curing conditions were the curing conditions for the actual structure. It is considered that the sealing and curing indicates the strength of the interior of the structure, and the curing in air indicates the strength of the surface of the structure. The cement compositions of the examples are expected to have improved strength in actual structures because the strength-improving effect in sealing/curing in air is significantly higher than that of the comparative examples in which no cement additive is added.

On the other hand, in comparative examples 9 to 16 using a powdery water-absorbent resin in which the anionic monomer is more than 20 mol% in the monomer mixture (comparative production example 1) and comparative example 17 using a powdery water-absorbent resin in which the nonionic crosslinking monomer is less than 0.1 mol% in the monomer mixture (comparative production example 4), it is necessary to mix a large amount of the dispersant in order to obtain the same flow value (fluidity). Further, the cement compositions of comparative examples 9 to 17 showed high viscosity due to long flowing-down time, and as a result, they were inferior in handling.

[ evaluation method 3: concrete test and Strength test method

Ordinary portland cement (manufactured by pacific cement corporation) was used as cement, land sand produced in the great shaft and river system was used as fine aggregate, crushed stone produced in the Qinghai world was used as coarse aggregate, tap water was used as kneading water, and cement: 382kg/m³And water: 172kg/m³Fine aggregate: 796kg/m³And coarse aggregate: 930kg/m³Fine aggregate ratio (fine aggregate/fine coarse aggregate + coarse aggregate) (volume ratio): a cement composition was prepared by blending 47% of a dispersant for cement and a powdery water-absorbent resin at a blending ratio (water/cement ratio (mass ratio)) of 0.45 as shown in Table 3 below. The powdery water-absorbent resin was previously added in an amount of 0.3 parts by mass per 100 parts by mass of cement and mixed with the cement.

The materials used for the measurement, the forced stirring mixer, and the measuring instruments were subjected to temperature adjustment under the above-mentioned measuring temperature atmosphere so that the temperature of the cement composition became the measuring temperature of 20 ℃. In order to avoid the influence of air bubbles in the cement composition on the fluidity of the cement composition, an oxyalkylene-based defoaming agent is used as necessary, and the amount of air is adjusted so as to be 4.5. + -. 0.5%.

Concrete was produced using a forced-stirring mixer under the above conditions for a kneading time of 90 seconds, and the flow value and the air amount were measured. The flow value and the air amount were measured in accordance with Japanese Industrial standards (JIS-A-1101: 2014, 1128: 2014). The amount of the cement dispersant added is an amount such that the fluidity is 375mm to 425 mm.

After the flow value and the air amount were measured, a sample for a compressive strength test was prepared, and the compressive strength after 28 days was measured under the following conditions.

Preparing a test body: 100mm x 200mm

Maintenance of the test body (28 days): after curing at about 20 ℃ and 60% humidity in constant temperature and humidity air for 24 hours, the test piece was wrapped with a polyethylene film so that water could not be exchanged between the concrete surface and the outside, and then the test piece was placed in a polyethylene bag and sealed, and sealing and curing were carried out for 27 days.

Polishing a test body: surface polishing of test body (use polishing finishing machine of test body)

And (3) measuring the compressive strength: automatic compression strength tester (Qianchuan manufacturing institute)

The results are shown in table 3 below.

[ evaluation method 4: funnel flow-down test method

As evaluation of piping passability in pumping, a funnel flow test of mortar was performed. The mortar was judged to have good piping passability without blocking in the middle and flowing down in a short time. The specific method of the funnel flow-down test is as follows.

As an index indicating the viscosity of concrete, the V-funnel flow-down time of freshly poured concrete immediately after filling was measured using a V-funnel according to "the flow-down test method (case) using a funnel for high-fluidity concrete (JSCE-F512-2007)" (edited by the ministry of association of standards of the concrete committee of the institute of civil engineering, "the standard specification of concrete was set in 2007 (" japanese text of the norm ": display a square 26360) [ reference of the article of basic science and association standards", association of the society of law with the civil engineering, 5 months, first printing, p.198-199, in 19 years, by the platonic society of societies.

The results are shown in table 3 below. In the column of the flow-down time in table 3, "block" means: the viscosity is too high, and the concrete is blocked in the V-shaped funnel and does not flow out completely.

[ Table 3]

From the above results, it is known that: the cement compositions using the cement additives of the examples obtained the same flow values at the same or smaller dispersion amounts than those of comparative example 18 without the cement additives. In addition, the cement compositions using the cement additives of examples were smaller in the amount of the cement dispersant than the cement compositions using the cement additives of comparative examples 19 to 21, among the cement compositions having the same flow value (fluidity). Further, the cement compositions using the cement additives of the examples showed low viscosity and excellent pump transportability, because the flow-down time was short. The cement compositions using the cement additives of the examples were improved in sealing strength and curing strength in air over 28 days, as compared with comparative example 18 in which no cement additive was added.

On the other hand, in comparative examples 19 to 21 using powdery water-absorbent resins (comparative production examples 1 to 3) in which the anionic monomer is present in an amount exceeding 20 mol% in the monomer mixture, it is necessary to add a large amount of a dispersant in order to obtain an equivalent flow value (fluidity). Further, the cement compositions of comparative examples 19 to 21 showed high viscosity due to long flowing-down time, and as a result, they were inferior in handling.

The present application is based on japanese patent application No. 2019-074148, filed on 9/4/2019, the disclosure of which is incorporated in the present specification by reference in its entirety.