JP6906265B1 - Additives for hydraulic compositions and hydraulic compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To appropriately adjust the amount of air in a hydraulic composition with little change in fluidity with time, regardless of the operating temperature, by adding the hydraulic composition. Provided is an additive for a hydraulic composition which does not excessively delay the setting time. An additive for a hydraulic composition, which comprises a predetermined A component and a predetermined B component. [Selection diagram] None

Description

The present invention relates to an additive for a hydraulic composition and a hydraulic composition. More specifically, the present invention relates to an additive for a hydraulic composition added to a hydraulic composition such as concrete, and a hydraulic composition to which the additive is added.

Conventionally, a cured product such as concrete is produced by filling a hydraulic composition into a predetermined mold and then curing the product.

It is important that this hydraulic composition has sufficient fluidity from the viewpoint of workability such as filling into a mold.

Therefore, additives for improving the fluidity of the hydraulic composition have been developed. Specifically, an initial slump long-term maintenance agent such as concrete composed of a predetermined setting retarder such as gluconic acid and a predetermined high-performance AE water reducing agent such as aminosulfonic acid (see, for example, Patent Document 1). Those containing a polymer whose adsorption amount to cement and clay satisfy a predetermined condition (see, for example, Patent Document 2) have been reported.

Here, as described above, having sufficient fluidity from the viewpoint of workability such as filling into the mold is one of the important factors for the hydraulic composition, but on the other hand, filling After that, it is required that it condenses and hardens in a desired time (that is, in a relatively short time) and exhibits sufficient performance in terms of strength and the like.

It is not easy to satisfy both the retention of fluidity and the fact that the setting time is not excessively delayed, and in general, a hydraulic composition having good fluidity retention has a long setting time and is hardened. Often time is required. For this reason, an additive that does not excessively delay the setting time while maintaining the fluidity of the hydraulic composition has been developed.

Specifically, it has been reported that a specific polycarboxylic acid-based polymer is used as an additive (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 10-7445 Japanese Unexamined Patent Publication No. 2014-181171 Japanese Unexamined Patent Publication No. 2007-270072

However, although the additives such as the hydraulic composition described in Patent Documents 1 to 3 improve the state of fluidity, viscosity and the like in the hydraulic composition and the like, there is still room for improvement, and there is still room for improvement. The development of additives for hydraulic compositions has been sought. Specifically, there has been a demand for the development of an additive that does not excessively delay the setting time, while the change in fluidity with time is small and the amount of air can be adjusted as appropriate regardless of the operating temperature.

Therefore, in view of the above circumstances, the present invention has an additive (water-hardness) that does not excessively delay the setting time, while the change in fluidity with time is small and the amount of air can be adjusted as appropriate regardless of the operating temperature. It is an object of the present invention to provide an additive for a composition).

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a predetermined A component and B component. According to the present invention, the following additives for hydraulic composition and hydraulic composition are provided.

[1] The following component A and
Component B, which is a polymer compound containing a structure derived from a monomer having a naphthalene ring (excluding those encapsulated by the component A) ,
Contains ,
When the total content ratio of the A component and the B component is 100 parts by mass,
An additive for a hydraulic composition, which comprises 1 to 50 parts by mass of the component A and 50 to 99 parts by mass of the component B.
<Component A>
Polyallylamine, polyallylamine salts, di allylamine polymer, diallylamine salt polymers, diallylamine, sulfur dioxide copolymer, diallylamine salt-sulfur dioxide copolymer, and at least one selected from polyvinyl pyrrolidone.

(Delete)

[ 2 ] Further, the additive for a hydraulic composition according to the above [1], which contains a C component which is a compound represented by the following general formula (1).

（一般式（１）において、Ｒ^１はロジンのアシル残基である。Ｒ^２は、水素原子、炭素数１〜２０のアルキル基、又は炭素数２〜２０のアルケニル基である。ＡＯは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。ｍは、１〜２００の整数である。）

(In the general formula (1), R ¹ is an acyl residue of rosin. R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. AO is a hydrogen atom. It is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, it can be one kind alone or two or more kinds). M is an integer of 1 to 200).

[ 3 ] Assuming that − (AO) _m − in the general formula (1) is 100 mol% in total of the constituent ratios of the oxyalkylene groups having 2 to 4 carbon atoms.
The additive for a hydraulic composition according to the above [2 ], which has an oxyalkylene group having 2 carbon atoms in a proportion of 90 mol% or more.

[ 4 ] When the A component, the B component, and the C component are contained, and the total content ratio of the A component, the B component, and the C component is 100 parts by mass.
The water according to [2 ] or [ 3 ], which contains 1 to 50 parts by mass of the A component, 49 to 98 parts by mass of the B component, and 0.01 to 10 parts by mass of the C component. Additives for rigid compositions.

[ 5 ] The additive for a water-hard composition according to any one of [1] to [4 ] above, wherein the component B is a condensate of formaldehyde and at least one selected from naphthalene sulfonic acid and a salt thereof. ..

[ 6 ] A hydraulic composition comprising the additive for a hydraulic composition according to any one of the above [1] to [ 5].

The additive for a hydraulic composition of the present invention has an effect that the change in fluidity with time is small and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the setting time is not excessively delayed. It is a thing.

The hydraulic composition of the present invention has the effect that the fluidity does not change with time and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the setting time is not excessively delayed. ..

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that the following embodiments can be appropriately modified, improved, or the like based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, unless otherwise specified,% means mass% and parts means parts by mass.

(1) Additives for hydraulic composition:
The additive for a hydraulic composition of the present invention contains a predetermined component A and a component B, which is a polymer compound containing a structure derived from a monomer having a naphthalene ring. By blending such an additive for a hydraulic composition with the hydraulic composition, the hydraulic composition has little change in fluidity with time regardless of the operating temperature, and the amount of air can be adjusted as appropriate. It becomes. In particular, normally, in an environment of high temperature (for example, 30 ° C. or higher), the change in fluidity with time is large, and the higher the temperature, the faster the fluidity decreases. However, by adding the additive for the hydraulic composition of the present invention, the change in fluidity with time is reduced even in a high temperature environment. Therefore, it can be used satisfactorily even in a country or region where the operating temperature is high and the temperature is 30 ° C. or higher.

On the other hand, the hydraulic composition is required to be condensed in an appropriate time (that is, the setting time is not too long and is appropriate) due to the finishing with a trowel or the like and the demolding of the mold. Is desired). In this respect, the additive for a hydraulic composition of the present invention has an advantage that the setting time of the hydraulic composition is not excessively delayed regardless of the operating temperature. Here, to prevent the setting time from being excessively delayed, by adding an additive, the fluidity of the hydraulic composition is maintained for about several hours (for example, about 1 to 2 hours) after kneading, and the setting starts. However, on the other hand, the fluidity decreases and condensation starts within a few hours after kneading.

Specifically, it is sufficient if the ready-mixed concrete can be driven immediately after the production of the ready-mixed concrete (hydraulic composition), but usually, from the production of the ready-mixed concrete to the driving at the work site, the ready-mixed concrete factory It takes time such as transportation time from to the work site and waiting time at the work site. The time from this ready-mixed concrete factory to the work site may be about several hours. Therefore, it is desired that the mixture be held for several hours (for example, about 1 to 2 hours) after kneading. On the other hand, it is desirable that coagulation is started after the ready-mixed concrete is poured. As described above, it is desired that the fluidity is ensured for a predetermined time in consideration of the time for transportation and the like, and that the coagulation starts appropriately after the lapse of the predetermined time.

It is possible to maintain fluidity to some extent by using a large amount of existing retarding agents (for example, saccharides, oxycarboxylic acid salts, etc.). However, in that case, there is a problem that the condensation is excessively delayed and curing failure occurs. To solve such a problem, by using the additive for hydraulic composition of the present invention, fluidity can be maintained and excessive setting delay occurs as in the case of using a large amount of retarding agent. Can be prevented.

(1-1) Component A:
Component A is polyallylamine, polyallylamine salt, polyalkyleneimine, alkylene oxide adduct of polyalkyleneimine, diallylamine polymer, diallylamine salt polymer, diallylamine / sulfur dioxide copolymer, diallylamine salt / sulfur dioxide copolymer, And polyvinylpyrrolidone, at least one selected from polyallylamine, polyallylamine salt, diallylamine polymer, diallylamine salt polymer, diallylamine / sulfur dioxide copolymer, diallylamine salt / sulfur dioxide copolymer, and polyvinylpyrrolidone. be. By blending this component A together with component B, there is little change in fluidity over time and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the effect of not excessively delaying the setting time is exhibited. Will be done.

The component A is preferably at least one selected from polyallylamine, polyallylamine salt, and polyvinylpyrrolidone. At least one selected from polyallylamine, polyallylamine salt, and polyvinylpyrrolidone as the component A has a mass average molecular weight of 1,000 or more and preferably 1,200,000 or less, preferably 1,000 or more. It is more preferably 900,000 or less, and further preferably 1,000 or more and 300,000 or less.

(1-2) B component:
The B component is a polymer compound containing a structure derived from a monomer having a naphthalene ring. By blending this B component together with the A component, the change in fluidity with time is small and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the effect of not excessively delaying the setting time is exhibited. Will be done. However, in the present invention, the component B excludes those encapsulated in the component A.

The monomer having a naphthalene ring is not particularly limited, and examples thereof include naphthalene sulfonic acid and naphthalene sulfonate, and the polymer compound as the B component is derived from such a monomer. It contains a structure (monomer unit).

The polymer compound containing a structure derived from a monomer having a naphthalene ring is preferably a condensate of formaldehyde and at least one selected from naphthalene sulfonic acid and a salt thereof.

The mass average molecular weight of the polymer compound containing a structure derived from a monomer having a naphthalene ring can be 200,000 or less, preferably 100,000 or less, and preferably 80,000 or less. More preferably, it is particularly preferably 50,000 or less, and most preferably 30,000 or less. The mass average molecular weight of the polymer compound is preferably 1,000 or more, more preferably 3,000 or more, particularly preferably 4,000 or more, and 5,000 or more. Is most preferable.

The mass average molecular weight of the polymer compound containing the structure derived from the monomer having a naphthalene ring can be measured by gel permeation chromatography (GPC) under the following conditions.
[GPC conditions]
Column: G4000SWXL + G2000SWXL (manufactured by Tosoh)
Eluent: 50 mM CH ₃ COONa / CH ₃ CN = 6/4
Flow rate: 0.7 mL / min Detection: UV280 nm
Sample concentration: 0.2 mg / mL
Standard substance: PEG / PEO (manufactured by Agilent Technologies)

The condensate of at least one selected from naphthalene sulfonic acid and its salt among the B components and formaldehyde can be co-condensed with phenol, cresol, and derivatives thereof within a range that does not impair the performance. It may be co-condensed with a compound having an aromatic ring structure.

More specifically, the B component may include a sodium formaldehyde condensate of sodium naphthalene sulfonate (that is, a condensate of sodium naphthalene sulfonate and formaldehyde).

Further, as a condensate of formaldehyde and at least one selected from naphthalene sulfonic acid and a salt thereof among the B components, a commercially available product can also be used. Commercially available products of condensates of at least one of such naphthalene sulfonic acid and naphthalene sulfonate and formaldehyde include, for example, Paul Fein 510-AN (manufactured by Takemoto Yushi Co., Ltd.), Mighty 150 (manufactured by Kao Co., Ltd.), and Cellflow 110P. (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

(1-3) C component:
The additive for a hydraulic composition of the present invention preferably further contains a C component which is a compound represented by the following general formula (1). By further blending this C component, the change in fluidity with time is small and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the effect of not excessively delaying the setting time is exhibited. ..

（一般式（１）において、Ｒ^１はロジンのアシル残基である。Ｒ^２は、水素原子、炭素数１〜２０のアルキル基、又は炭素数２〜２０のアルケニル基である。ＡＯは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。ｍは、１〜２００の整数である。）

(In the general formula (1), R ¹ is an acyl residue of rosin. R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. AO is a hydrogen atom. It is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, it can be one kind alone or two or more kinds). M is an integer of 1 to 200).

^{R 1} in the general formula (1) is an acyl residue of rosin. Here, rosin refers to a diterpene compound called a resin acid (loginic acid). Examples of such rosins include natural rosins, modified rosins, and polymerized rosins.

Natural rosin is a mixture of resin acids present in the residue obtained by distilling volatile substances such as essential oils from resin oil obtained from Pinaceae plants, and is classified into gum rosin, wood rosin, and tall oil rosin according to the production method. Will be done.

Gumrosin is obtained by cutting a pine tree, filtering and refining the raw pine fat flowing out of the pine tree, and removing turpentine oil by steam distillation. Wood rosin is obtained by solvent-extracting pine stump chips. Tall oil rosin is obtained by distilling and refining crude tall oil produced as a by-product in the process of producing pulp from pine wood by the kraft pulp method.

Login contains abietic acid as the main component resin acid, and neo-avietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimalic acid, isopimalic acid, sandalacopimaric acid, levopimal as the resin acids of other components. Contains acids and the like.

The modified rosin refers to a modified natural rosin. For example, the natural rosin is hydrogenated using a noble metal catalyst such as a nickel catalyst, a platinum catalyst, or a palladium catalyst at high pressure to form a double bond in the molecule. Examples thereof include hydrogenated rosin in which hydrogenated rosin is eliminated or reduced, and disproportionated rosin in which unstable conjugated double bonds in the molecule are eliminated by heating natural rosin at a high temperature in the presence of a noble metal catalyst or a halogen catalyst.

The polymerized rosin is a reaction between natural rosins or modified rosins, and refers to these dimers and trimers.

As such rosin, natural rosin is preferable from the viewpoint of easy availability. As such a natural rosin, gum rosin is more preferable. Rosin is generally treated as a mixture of various compounds, and the amount of carboxylic acid is quantified by measuring the acid value. The acid value is determined by measuring according to the Japanese Industrial Standards JIS K 0070 (1992).

^{R 2} in the general formula (1) is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group. , N-octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group and other linear or branched alkyl groups. Examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, an n-propenyl group, an n-butenyl group, an n-pentenyl group, an n-hexenyl group, an n-heptenyl group, an n-octenyl group, an n-nonel group and n. -Desenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenyl group, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-octadecenyl group, n-nonadesenyl group, n -Icosenyl group and the like can be mentioned. Among these, alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and n-pentyl group, ethenyl group, n Alkyl groups having 2 to 5 carbon atoms such as −propenyl group, n-butenyl group and n-pentenyl group are preferable.

The AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one kind alone or two or more kinds can be used), and the AO has two carbon atoms. Examples of the oxyalkylene group of ~ 4 include an oxyethylene group, an oxypropylene group, and an oxybutylene group.

When there are two or more types of AO, it may be in any form of a random adduct, a block adduct, and an alternate adduct.

M in the general formula (1) is an integer of 1 to 200, preferably an integer of 1 to 150, and more preferably an integer of 5 to 100.

_{The C component contains 90 mol of an oxyalkylene group having 2 carbon atoms, where − (AO) m} − in the general formula (1) is 100 mol% in total of the constituent ratios of the oxyalkylene groups having 2 to 4 carbon atoms. It is preferable to have a ratio of% or more.

The method for producing the compound represented by the general formula (1) is not particularly limited. For example, by using a catalyst or the like for rosin, which is a mixture of resin acids such as abietic acid, neoavietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimaric acid, isopimalic acid, sandaracopimalic acid, and levopimalic acid By a method of adding an alkylene oxide by a conventional method to produce a rosin polyoxyalkylene adduct represented by the general formula (1), or by using a catalyst or the like in advance for an alcohol corresponding to ^{R 2 by a conventional method.} Examples thereof include a method for producing a compound represented by the general formula (1) by adding an alkylene oxide and then esterifying it with rosin.

(1-4) Mixing ratio of each component:
In the present invention, when the A component and the B component are contained (provided that the C component is not contained) and the total content ratio of the A component and the B component is 100 parts by mass, the A component is 1 to 50 parts by mass. and B components you contained in a ratio of 50 to 99 parts by weight. Within such a range, the change in fluidity with time is further reduced regardless of the operating temperature.

When the total content of the A component, the B component, and the C component is 100 parts by mass, the A component is 1 to 50 parts by mass and the B component is 49 to 98 parts by mass. It is preferable that the portion and the C component are contained in a ratio of 0.01 to 10 parts by mass. Within such a range, the change in fluidity with time is further reduced regardless of the operating temperature.

(1-5) Other ingredients:
The additive for a hydraulic composition of the present invention may further contain other components in addition to the components A to C as long as the effect is not impaired. Examples of such other components include saccharides, a setting retarding component made of oxycarboxylate and the like, a component having a dispersing action made of sodium lignin sulfonate and the like, an AE agent made of an anionic surfactant and the like, and oxy. Antifoaming agent made of alkylene compounds, curing accelerator made of alkanolamine, shrinkage reducing agent made of polyoxyalkylene alkyl ether, thickener made of cellulose ether compound, preservative made of isothiazolin compound, etc. , A rust preventive composed of nitrite and the like.

The content ratio of the other components may be, for example, 0 to 20% by mass of the total additive for the hydraulic composition of the present invention.

Further, the additive for a hydraulic composition of the present invention may be used in a form diluted with water or a solvent.

(2) Hydraulic composition:
The hydraulic composition of the present invention contains the additive for the hydraulic composition of the present invention. In such a hydraulic composition, the fluidity does not change with time and the amount of air can be adjusted as appropriate regardless of the operating temperature, while the setting time is not excessively delayed.

In the water-hard composition of the present invention, the content ratio of the additive for the water-hard composition of the present invention is not particularly limited and can be appropriately set. For example, 0.001 to 0.001 to the binder in terms of solid content. 4.0% by mass is preferable, and 0.01 to 4.0% by mass is more preferable.

The hydraulic composition of the present invention may contain a binder, water, fine aggregate, and coarse aggregate in the same manner as the conventionally known hydraulic composition.

Examples of the binder include various Portland cements such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, early strength Portland cement, and sulfate resistant Portland cement, and various cements such as blast furnace cement, fly ash cement, and silica fume cement. Can be mentioned.

Further, as the binder, various admixtures such as fly ash, blast furnace slag fine powder, limestone fine powder, stone powder, silica fume, and expansion material may be used in combination with the above-mentioned various cements.

Examples of the fine aggregate include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, and various slag fine aggregates.

Examples of the coarse aggregate include river gravel, mountain gravel, land gravel, crushed stone, various slag coarse aggregates, and lightweight aggregates.

The hydraulic composition of the present invention may further contain other components as appropriate, as long as the effect is not impaired. Examples of such other components include saccharides, a setting retarding component made of oxycarboxylate and the like, a component having a dispersing action made of sodium lignin sulfonate and the like, an AE agent made of an anionic surfactant and the like, and oxy. Antifoaming agent made of alkylene compound, etc., curing accelerator made of alkanolamine, etc., shrinkage reducing agent made of polyoxyalkylene alkyl ether, etc., thickener made of cellulose ether compound, etc., preservative made of isothiazoline compound, etc. , A rust preventive composed of nitrite and the like.

The content ratio of the other components may be, for example, 0 to 5% by mass in terms of solid content with respect to the binder.

In the hydraulic composition of the present invention, a conventionally known ratio can be appropriately adopted as the ratio of the water to the binder (water / binder ratio).

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

First, the components A to C used are shown in Tables 1 to 3 below.

(Component A)
Table 1 below shows the A components (A-1 to A-11) used.

(Synthesis Example 1) Production method of A-8:
A-8 in Table 1 was manufactured as follows. First, 2000 g of A-7 tetraethylenepentamine was placed in a 5 L stainless steel pressure-resistant container. Then, after nitrogen substitution, 930 g of ethylene oxide was press-fitted at 75 ± 5 ° C. under the condition of 0.3 MPa or less, and aged at the same temperature for 1 hour. After cooling, it was recovered to obtain A-8 (component A).

(B component)
Table 2 below shows the B components (B-1 to B-2) used.

(C component)
Table 3 below shows the C components (C-1 to C-5) and CR-1 used.

In Table 3, as "CR-1", X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in the People's Republic of China (hereinafter, simply referred to as "produced in China") was used.

Further, in Table 3, "EO" represents an oxyethylene group and "PO" represents an oxypropylene group.

The method for synthesizing the C component (C-1 to C-5) will be described below.

(Synthesis Example 2) Synthesis of C-1:
In a 2 L stainless steel pressure-resistant container, 542.2 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were charged, heated to 120 ° C, and stirred. Dehydration under reduced pressure was performed for 1 hour. The pressure was returned to normal pressure with nitrogen, and then 1455.8 g of ethylene oxide was press-fitted at 150 to 160 ° C. under the condition of 0.4 MPa, and the mixture was aged at the same temperature for 1 hour. Then, the mixture was cooled, 3.5 g of 90% acetic acid was added, dehydration was performed under reduced pressure at 120 ° C., and pressure filtration was performed to obtain compound (C-1).

(Synthesis Example 3) Synthesis of C-2:
79.8 g of α-butoxy-ω-hydroxy-poly- (45 mol) oxyethylene 500.0 g and X grade (acid value: 171 mgKOH / g) of Chinese "gamrosin" in a 1 L glass reaction vessel. 7.2 g of methanesulfonic acid was charged, and after nitrogen substitution, dehydration was carried out under reduced pressure at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound C-2.

(Synthesis Example 4) Synthesis of C-3:
In a 2 L stainless steel pressure-resistant container, 192.2 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were charged, heated to 120 ° C, and stirred. Dehydration under reduced pressure was performed for 1 hour. The pressure was returned to normal pressure with nitrogen, and then 1805.8 g of ethylene oxide was press-fitted at 150 to 160 ° C. under the condition of 0.4 MPa, and the mixture was aged at the same temperature for 1 hour. Then, the mixture was cooled, 20.0 g of an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyoward 600) was added, dehydrated under reduced pressure at 120 ° C., and then pressure-filtered to obtain compound (C-3).

(Synthesis Example 5) Synthesis of C-4:
In a 2 L stainless steel pressure-resistant container, 626.2 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were charged, heated to 120 ° C, and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 1260.9 g of ethylene oxide was press-fitted at 150 to 160 ° C. under the condition of 0.4 MPa, and then 110.9 g of propylene oxide was press-fitted under the same conditions, and the temperature was unchanged for 1 hour. Aged. Then, the mixture was cooled, 20.0 g of an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyoward 600) was added, dehydrated under reduced pressure at 120 ° C., and then pressure-filtered to obtain compound (C-4).

(Synthesis Example 6) Synthesis of C-5:
In a 2 L stainless steel pressure-resistant container, 966.1 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were charged, heated to 120 ° C, and stirred. Dehydration under reduced pressure was performed for 1 hour. After returning to normal pressure with nitrogen, 518.8 g of ethylene oxide was press-fitted at 150 to 160 ° C. under the condition of 0.4 MPa, and then 513.2 g of propylene oxide was press-fitted under the same conditions, and the temperature was unchanged for 1 hour. Aged. Then, the mixture was cooled, 3.5 g of 90% acetic acid was added, dehydration was performed under reduced pressure at 120 ° C., and pressure filtration was performed to obtain compound (C-5).

(Examples 1 to 6 , 10 to 15, Comparative Examples 1 and 2, Reference Examples 7 to 9, 16)
Next, as shown in Table 4, each component was mixed to prepare an additive for a hydraulic composition. In Table 4, the mass part of "water" indicates the mass part with respect to 100 parts by mass of the additive for hydraulic composition.

(Examples 17 to 22, 26 to 31 , Comparative Examples 3 to 6 , Reference Examples 23 to 25, 32 )
Next, each hydraulic composition shown in Table 5 was prepared by using the prepared additive for hydraulic composition and adopting Formulation 1 shown in Table 6.

Specifically, a hydraulic composition (concrete composition) was prepared as follows. First, in a 55L forced twin-screw mixer, ordinary Portland cement as cement (manufactured by Pacific Cement, density = 3.16 g / cm ³ ) and Chubu fly ash as fly ash (manufactured by Techno Chubu, density = 2. 33 g / cm ³ , JIS A 6201 fly ash type II) and Esment 4000 as blast furnace slag fine powder (manufactured by Nittetsu Portland Cement, density = 2.89 g / cm ³ , JIS A 6206 blast furnace slag fine powder 4000) Table 6 shows fine aggregate as aggregate (land sand from Oigawa water system, density = 2.58 g / cm ³ ) and coarse aggregate (crushed stone from Okazaki, density = 2.66 g / cm ^3). Formulation (Formulation 1) Formulated. Then, the additives for each hydraulic composition (F-1 to 16, FR-1, 2) are blended therein, and Examples 17 to 22, 26 to 31 , Comparative Examples 3 to 6 , and Reference Examples 23 to 23. 25 and 32 hydraulic compositions were prepared (see Table 4).

The hydraulic compositions of Examples 17 to 22, 26 to 31 , Comparative Examples 3 to 6 , and Reference Examples 23 to 25 , 32 are kneaded by adjusting the amount of the aqueous additive solution for the hydraulic composition. Immediately after, make sure that the slump is within the range of 21.0 ± 1.5 cm, use a commercially available AE agent AE-300 (manufactured by Takemoto Yushi Co., Ltd.) as appropriate, and use an antifoaming agent AFK-2 (Takemoto). (Manufactured by Yushi) was used in an amount of 0.001% by mass based on the binder, and the amount of air was adjusted to be within the range of 1.5 ± 1.0%.

Further, each hydraulic composition is prepared in an environment of 20 ° C. and 30 ° C., respectively, and before preparation, the kneading temperature of each hydraulic composition is within ± 2 ° C. of each environmental temperature. The temperature of each material was adjusted.

The formulation 1 adopted in Examples 17 to 22, 26 to 31 , Comparative Examples 3 to 6 , and Reference Examples 23 to 25, 32 is a formulation using cement as the hydraulic powder.

Next, the slump (cm), the amount of air (volume%), and the concrete temperature (° C.) were measured for each of the produced hydraulic composition (concrete composition). The results are shown in Table 5 below. The measured values under the environment of 20 ° C. and the environment of 30 ° C. are shown. In Table 5, "slump (cm)" means slump (cm) immediately after kneading, "air amount (%)" means air amount (%) immediately after kneading, and "concrete temperature (concrete temperature (%)". ℃) ”means the temperature (° C) of the concrete immediately after kneading.

・ Slump (cm):
The concrete composition was measured according to JIS-A1101 (2020).

・ Air volume (volume%):
The concrete composition was measured according to JIS-A1128 (2020).

・ Concrete temperature (℃):
The concrete composition was measured according to JIS-A1156 (2014).

In Comparative Example 5, the amount of air was equal to or more than the specified amount even when the defoaming agent AFK-2 was used in an amount of 0.005% by mass with respect to the binder without using the AE agent. The retarder aqueous solution was prepared by mixing 400 g of sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.), 100 g of sucrose (reagent: manufactured by Kishida Chemical Co., Ltd.), and 500 g of ion-exchanged water.

(Evaluation results)
For each of the prepared hydraulic compositions, the flow retention was evaluated and the setting time was evaluated.

(Flow retention)
Immediately after kneading (after 0 minutes) and 90 minutes after kneading, the slump (cm) was measured by the above measurement method, respectively, and then, based on the obtained measured values, "0 minutes and 90 minutes". Later slump difference "was calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as the evaluation of flow retention. Table 7 shows the evaluation results of the flow retention in the environment of 20 ° C., and Table 8 shows the evaluation results of the flow retention in the environment of 30 ° C.

-Slump difference between 0 minutes and 90 minutes S: Difference 4.0 cm or less A: Difference more than 4.0 cm, 7.0 cm or less B: Difference more than 7.0 cm, 10.0 cm or less C: Difference 10 More than 0.0 cm, less than 13.0 cm D: Difference more than 13.0 cm, 16.0 cm or less E: Difference more than 16.0 cm

(Condensation time)
For each hydraulic composition (concrete composition) produced, the settling start time was measured as follows, and then the settling time was evaluated. Table 7 shows the evaluation results of the settling start time in an environment of 20 ° C., and Table 8 shows the evaluation results of the settling start time in an environment of 30 ° C.

・ Condensation start time:
Using the concrete composition immediately after kneading, the settling start time was measured according to JIS-A1147 (2019).

The evaluation criteria for the evaluation of the onset time of condensation under the environment of 20 ° C. and 30 ° C. are shown below.

・ Condensation time (under 20 ℃ environment)
A: Condensation start time is within 6 and a half hours B: Condensation start time is over 6 and a half hours, 7 and a half hours C: Condensation start time is over 7 and a half hours

・ Condensation time (under 30 ° C environment)
A: Condensation start time is within 6 hours B: Condensation start time is over 6 hours, 7 hours or less C: Condensation start time is over 7 hours

As shown in Comparative Example 4, in the case of an additive for a hydraulic composition that does not contain the component A, a comparison between a 20 ° C. environment and a 30 ° C. environment shows that the temperature is 30 ° C. However, it can be seen that the slump difference becomes large and the fluidity greatly decreases in a high temperature environment. Further, in Comparative Example 5, as described above, even if the defoaming agent AFK-2 was used in an amount of 0.005% by mass with respect to the binder without using the AE agent, the amount of air became equal to or more than the specified amount, and the amount of air In Tables 7 and 8, "-" is shown because the adjustment was not possible due to the excess.

(Example 33, Comparative Examples 7 and 8)
Next, using the prepared additive for the hydraulic composition, the formulation 2 shown in Table 10 was adopted, the same method for preparing the hydraulic composition as the above-mentioned formulation 1, the same slump, and the amount of air. Each hydraulic composition shown in Table 9 was prepared using the adjustment method of. The formulation 2 adopted in Example 33 and Comparative Examples 7 and 8 is a formulation using cement, fly ash, and blast furnace slag fine powder as the hydraulic powder.

Next, for each of the prepared hydraulic compositions (concrete composition), the same measurement method as in Formulation 1 described above was adopted, and the slump (cm), the amount of air (volume%), and the concrete temperature (° C.) Was measured. The results are shown in Table 9 below. The measured values under the environment of 20 ° C. and the environment of 30 ° C. are shown. In Table 9, "slump (cm)" means slump (cm) immediately after kneading, "air amount (%)" means air amount (%) immediately after kneading, and "concrete temperature (concrete temperature (%)". ℃) ”means the temperature (° C) of the concrete immediately after kneading.

In Table 9, the retarder aqueous solution was prepared by mixing 400 g of sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.), 100 g of sucrose (reagent: manufactured by Kishida Chemical Co., Ltd.), and 500 g of ion-exchanged water.

(Evaluation results)
For each of the prepared hydraulic compositions, the flow retention was evaluated and the setting time was evaluated.

(Flow retention)
Immediately after kneading (after 0 minutes) and 90 minutes after kneading, the slump (cm) was measured by the above measurement method, respectively, and then, based on the obtained measured values, "0 minutes and 90 minutes". Later slump difference "was calculated. Then, these "slump differences" were evaluated according to the following evaluation criteria, and this was used as the evaluation of flow retention. Table 11 shows the evaluation results of the flow retention in the environment of 20 ° C., and Table 12 shows the evaluation results of the flow retention in the environment of 30 ° C.

-Slump difference between 0 minutes and 90 minutes S: Difference 3.0 cm or less A: Difference more than 3.0 cm, 6.0 cm or less B: Difference more than 6.0 cm, 9.0 cm or less C: Difference 9 More than 0.0 cm and less than 12.0 cm D: Difference is more than 12.0 cm

(Condensation time)
For each hydraulic composition (concrete composition) produced, the settling start time was measured as follows, and then the settling time was evaluated. Table 11 shows the evaluation results of the settling start time in an environment of 20 ° C., and Table 12 shows the evaluation results of the settling start time in an environment of 30 ° C.

・ Condensation start time:
Using the concrete composition immediately after kneading, the coagulation start time was measured by adopting the same measuring method as in Formulation 1 described above.

The evaluation criteria for the evaluation of the onset time of condensation under the environment of 20 ° C. and 30 ° C. are shown below.

・ Condensation time (under 20 ℃ environment)
A: Condensation start time is within 7 and a half hours B: Condensation start time is over 7 and a half hours, 8 and a half hours C: Condensation start time is over 8 and a half hours

・ Condensation time (under 30 ° C environment)
A: Condensation start time is within 7 hours B: Condensation start time is over 7 hours, 8 hours or less C: Condensation start time is over 8 hours

(result)
As shown in Tables 7, 8, 11, and 12, the hydraulic composition of the present invention is blended with the hydraulic composition, regardless of the environmental temperature at the time of use. It was confirmed that a hydraulic composition can be obtained in which the change in fluidity of the product with time is small and the amount of air can be adjusted as appropriate, while the setting time of the hydraulic composition is not excessively delayed. Further, the hydraulic composition of the present invention contains the additive for the hydraulic composition of the present invention, so that the fluidity of the hydraulic composition does not change with time regardless of the environmental temperature at the time of use and air. It was confirmed that the amount can be adjusted as appropriate, while the setting time is not excessively delayed.

The additive for a hydraulic composition of the present invention can be used as an additive added to a hydraulic composition such as concrete. Further, the hydraulic composition of the present invention can be used for producing a cured product such as concrete.

Claims (6)

The following A component and
Component B, which is a polymer compound containing a structure derived from a monomer having a naphthalene ring (excluding those encapsulated by the component A) ,
Contains ,
When the total content ratio of the A component and the B component is 100 parts by mass,
An additive for a hydraulic composition, which comprises 1 to 50 parts by mass of the component A and 50 to 99 parts by mass of the component B.
<Component A>
Polyallylamine, polyallylamine salts, di allylamine polymer, diallylamine salt polymers, diallylamine, sulfur dioxide copolymer, diallylamine salt-sulfur dioxide copolymer, and at least one selected from polyvinyl pyrrolidone. The additive for a hydraulic composition according to claim 1, further containing a C component which is a compound represented by the following general formula (1).

(In the general formula (1), R ¹ is an acyl residue of rosin. R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. AO is a hydrogen atom. It is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, it can be one kind alone or two or more kinds). M is an integer of 1 to 200). _{Assuming that − (AO) m} − in the general formula (1) is 100 mol% in total of the constituent ratios of the oxyalkylene groups having 2 to 4 carbon atoms.
The additive for a hydraulic composition according to claim 2 , which has an oxyalkylene group having 2 carbon atoms in a proportion of 90 mol% or more. When the A component, the B component, and the C component are contained, and the total content ratio of the A component, the B component, and the C component is 100 parts by mass.
The hydraulic composition according to claim 2 or 3 , which contains 1 to 50 parts by mass of the A component, 49 to 98 parts by mass of the B component, and 0.01 to 10 parts by mass of the C component. Additives for. The additive for a water-hard composition according to any one of claims 1 to 4 , wherein the component B is a condensate of formaldehyde and at least one selected from naphthalene sulfonic acid and a salt thereof. A hydraulic composition comprising the additive for a hydraulic composition according to any one of claims 1 to 5.