JP7307954B2 - cement composition - Google Patents

Description

The present invention relates to cement compositions. More particularly, it relates to low viscosity cement compositions.

Conventionally, cement compositions have been widely used for civil engineering and construction. In recent years, there has been a growing trend toward taller and larger-scale buildings. A strength cement composition is needed.

In general, in order to improve the compressive strength of a cement composition, it is conceivable to lower the water-binder ratio. will decline. Therefore, in order to realize such a high-strength cement composition and an ultra-high-strength cement composition, while reducing the water binder ratio, silica fume is used to suppress the increase in viscosity while suppressing the compressive strength. is proposed to be increased (see, for example, Patent Document 1). In addition, it has been proposed to use specific Portland cement and silica fume in order to ensure good fluidity even if the water-binder ratio is low (see, for example, Patent Document 2).

JP-A-5-58701 JP 2008-81357 A

However, although the cement compositions disclosed in Patent Documents 1 and 2 have a certain effect of reducing the viscosity of the silica fume contained therein, there is a problem that the effect is limited and the cement composition is expensive. In addition, the smaller the water-binder ratio, the greater the proportion of the powder that increases the viscosity relative to the dispersion medium, water, further reducing the flowability and, as a result, increasing the viscosity. was there.

In view of the above circumstances, it is an object of the present invention to provide a cement composition that has low viscosity even with a small amount of water, is less expensive than conventional ones, does not change the amount of air, and has high or ultra-high strength after curing. and

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that a cement composition having a specific composition is particularly suitable. According to the present invention, the following cement composition is provided.

[1] Contains a compound represented by the following general formula (1) obtained by adding an alkylene oxide to the resin acid of rosin, which is a mixture of resin acids , Portland cement, silica fume, water, a dispersant, and an antifoaming agent. and
A cement composition having a water binder ratio of 0.05 to 0.30 .

（但し、一般式（１）中、Ｒ^１は、ロジンに含まれる樹脂酸のアシル残基又は水素原子を示し（但し、ｎが１の場合、Ｒ^１はロジンに含まれる樹脂酸のアシル残基を示し、ｎが２以上の場合、Ｒ^１のうち、少なくとも１つはロジンに含まれる樹脂酸のアシル残基を示す）、Ｒ^２は、水素原子、ロジンに含まれる樹脂酸のアシル残基、炭素数１～２０のアルキル基、炭素数２～２０のアルケニル基、炭素数３～２０の多価アルコールから水酸基を除いた残基、炭素数１～２０のアシル基又は炭素数２～２０の多価カルボン酸のアシル残基を示し（但し、Ｒ^１の少なくとも一つが水素原子を示す場合、Ｒ^２は、水素原子以外の置換基を示す）、ＡＯは、炭素数２～１８のオキシアルキレン基を示し、ｍは１～２００の数であって、ｎは１～２０の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～２００となる関係を満たす数であり、ＡＯの内、炭素数２又は３のオキシアルキレン基が５０モル％以上である。）

(However, in general formula (1), R ¹ represents an acyl residue of resin acid contained in rosin or a hydrogen atom (provided that when n is 1, R ¹ represents an acyl residue of resin acid contained in rosin. and when n is 2 or more, at least one of ^R1 is an acyl residue of a resin acid contained in rosin), ^R2 is a hydrogen atom, an acyl residue of a resin acid contained in rosin group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 3 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms 20 polyvalent carboxylic acid acyl residue (however, when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom); represents an oxyalkylene group, m is a number of 1 to 200, n is a number of 1 to 20, and the above m and n are numbers satisfying the relationship m × n = 1 to 200 and 50 mol% or more of AO having 2 or 3 carbon atoms is an oxyalkylene group.)

[2] The cement composition according to [1] above, wherein the AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms.

[3] The cement composition according to [1] or [2] above, wherein R ¹ in the general formula (1) is an acyl residue of natural rosin.

[4] The cement composition according to any one of [1] to [3], wherein 90 mol% or more of the AO in the general formula (1) is an oxyalkylene group having 2 to 3 carbon atoms. .

[5] The n in the general formula (1) is a number from 1 to 6, and the m and n are numbers satisfying the relationship m × n = 1 to 100, the [1 ] The cement composition according to any one of [4].

[6] R ² in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a polyvalent group having 3 to 6 carbon atoms. Any one of the above [1] to [5], which represents a residue obtained by removing a hydroxyl group from an alcohol (provided that when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom). The cement composition according to .

[7] The cement composition according to any one of [1] to [6] above, wherein R ¹ in general formula (1) is an acyl residue of gum rosin.

[8] The cement composition according to any one of [1] to [7], wherein 50 mol % or more of the AO in the general formula (1) is an oxyalkylene group having 2 carbon atoms.

[9] The n in the general formula (1) is a number of 1 to 3, and the m and n are numbers satisfying the relationship m × n = 5 to 60, wherein the [1 ] The cement composition according to any one of [8].

[10] R ² in the general formula (1) is a hydrogen atom, an acyl residue of gum rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a polyvalent group having 3 to 6 carbon atoms. any of the above [1] to [9], which represents a residue obtained by removing a hydroxyl group from an alcohol (provided that when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom); The cement composition according to .

[11] The above [1] to [10], wherein the compound represented by the general formula (1) is contained in a proportion of 0.00001 to 1 part by mass per 100 parts by mass of Portland cement and silica fume. A cement composition according to any one of the above.

[12] The above [1] to [10], wherein the compound represented by the general formula (1) is contained in a proportion of 0.00005 to 0.4 parts by mass per 100 parts by mass of Portland cement and silica fume. ] The cement composition according to any one of

[13] The above [1] to [10], wherein the compound represented by the general formula (1) is contained in a proportion of 0.0001 to 0.1 part by mass per 100 parts by mass of Portland cement and silica fume. ] The cement composition according to any one of

[14] The cement composition according to any one of [1] to [13], wherein the dispersant is a polycarboxylic acid-based dispersant.

[15] The cement composition according to any one of [1] to [14], wherein the antifoaming agent is a polyether antifoaming agent.

The cement composition of the present invention has low viscosity even with a small amount of water, is less expensive than conventional cement compositions, has no change in air content, and has high or ultra-high strength after curing.

Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that modifications, improvements, etc., can be made to the following embodiments as appropriate 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, % means % by mass, and part means part by mass, unless otherwise specified.

(1) cement composition:
The cement composition of the present invention contains the compound represented by formula (1), Portland cement, silica fume, water, a dispersant and an antifoaming agent. Such cement compositions can be made less viscous with a small amount of water, have no change in air content, and have high or ultra-high strength after curing.

(1-1) Compound represented by general formula (1):
The cement composition of the present invention contains a compound represented by the following general formula (1) obtained by adding an alkylene oxide to the resin acid of rosin, which is a mixture of resin acids. This compound is also called a rosin polyoxyalkylene adduct.

R ¹ in general formula (1) is an acyl residue or a hydrogen atom of a resin acid contained in rosin. Here, rosin refers to a diterpenoic acid-based compound called resin acid (rosin acid).

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 off volatile substances such as essential oils from resin oil obtained from plants of the Pinaceae family. It is classified into gum rosin, wood rosin and tall oil rosin according to the manufacturing method. be done.

Gum rosin is obtained by cutting a pine tree, filtering and purifying raw pine resin flowing out from the cut, and removing turpentine oil by steam distillation.

Wood rosin is obtained by solvent extraction of pine stump chips.

Tall oil rosin is obtained by distilling and refining crude tall oil, which is a by-product in the process of producing pulp from pine wood by the kraft pulp method.

Rosin contains abietic acid as a main resin acid, and other resin acids such as neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, and sandaracopimaric acid. , levopimaric acid and the like.

A denatured rosin means a denatured natural rosin. For example, natural rosin is hydrogenated under high pressure using a nickel catalyst, platinum catalyst, palladium catalyst, or other noble metal catalyst to eliminate or reduce intramolecular double bonds. A disproportionated rosin in which unstable conjugated double bonds in the molecule are eliminated by heating at a high temperature in the presence of a catalyst or a halogen catalyst is mentioned.

Polymerized rosin is obtained by reacting natural rosin or modified rosin with each other, and refers to dimers and trimers thereof.

In the present invention, natural rosin is preferable as such rosin from the viewpoint of availability. Gum rosin is more preferred as such a natural rosin.

In general formula (1), AO is an oxyalkylene group having 2 to 18 carbon atoms. Examples of oxyalkylene groups having 2 to 18 carbon atoms include oxyethylene, oxypropylene, oxybutylene, oxytetramethylene, oxystyrene, oxydecylene, oxytetradecylene, and oxyhexadecylene. group, oxyoctadecylene group, and the like.

Among these, oxyalkylene groups having 2 to 4 carbon atoms such as oxyethylene group, oxypropylene group, oxybutylene group and oxytetramethylene group are preferable, and oxyalkylene groups having 2 to 3 carbon atoms such as oxyethylene group and oxypropylene group are preferable. An oxyalkylene group is more preferred. AO may be of one type or two or more types, and in the case of two or more types of AO, the oxyalkylene group may be in any form of random adduct, block adduct, or alternate adduct.

In the general formula (1), m represents the average number of added moles, m is a number of 1-200, preferably a number of 1-100, more preferably a number of 5-60.

n represents the number of added moles, n is a number from 1 to 20, preferably a number from 1 to 6, more preferably a number from 1 to 3.

m and n are numbers satisfying the relationship m×n=1 to 200, preferably numbers satisfying the relationship m×n=1 to 100, more preferably m×n=5 to 60. It is the number that satisfies the relationship. If the product of m and n exceeds 200, the manufacturing cost becomes too high and the viscosity of the cement composition becomes too high. Moreover, when the product of m and n is less than 1, the resulting cement composition has an excessive amount of air.

Further, in order to reduce the viscosity, it is necessary that the oxyalkylene group having 2 or 3 carbon atoms accounts for 50 mol % or more of AO in general formula (1). Preferably, oxyalkylene groups having 2 or 3 carbon atoms account for 90% or more. Furthermore, the content of oxyalkylene groups having 2 carbon atoms is preferably 50 mol% or more, more preferably 80 mol% or more, and most preferably oxyalkylene groups having 2 carbon atoms. 90 mol % or more. If the oxyalkylene group having 2 or 3 carbon atoms in AO is less than 50 mol %, the effect of the present invention cannot be obtained.

In formula (1), when n is 1, ^R1 is an acyl residue of resin acid contained in rosin. When n is 2 or more, at least one of R ¹ is an acyl residue of rosin.

In general formula (1), R ² is a hydrogen atom, an acyl residue of a resin acid contained in rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a polyacyl group having 3 to 20 carbon atoms. It is a residue obtained by removing a hydroxyl group from a hydric alcohol, an acyl group having 1 to 20 carbon atoms, or an acyl residue of a polyvalent carboxylic acid having 2 to 20 carbon atoms. However, when at least one of R ¹ represents a hydrogen atom, R ² is a substituent other than a hydrogen atom.

Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, n-octyl group, Linear or branched alkyl groups such as decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group can be mentioned. Among them, alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group are preferred.

Examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl and n-nonel groups. , n-decenyl 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-nonadecenyl group , n-icosenyl group and the like. Among them, alkenyl groups having 2 to 5 carbon atoms such as ethenyl group, n-propenyl group, n-butenyl group and n-pentenyl group are preferred.

Examples of residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 20 carbon atoms include residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 20 carbon atoms, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan. groups. Among them, residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 6 carbon atoms such as glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan are preferred.

Examples of acyl groups having 1 to 20 carbon atoms include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, and dodecanoyl. group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, icosanoyl group, 2-ethylhexanoyl group, 3-ethylheptanoyl group, 3- Linear or branched acyl groups such as ethyl decanoyl group and the like are included.

Examples of acyl residues of polycarboxylic acids having 2 to 20 carbon atoms include oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimeline acid, 2,2,6,6-tetramethylpimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, Acyl residues obtained by removing hydroxyl groups from aliphatic polycarboxylic acids having 2 to 20 carbon atoms such as eicosanedioic acid and 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid , dicyclohexyl-4,4'-dicarboxylic acid and acyl residues obtained by removing hydroxyl groups from alicyclic polycarboxylic acids having 6 to 20 carbon atoms such as camphoric acid, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4 , 4'-stilbenedicarboxylic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, orthophthalic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid and diphenylsulfonedicarboxylic acid. Examples include acyl residues obtained by removing hydroxyl groups from carboxylic acids. These acyl residues may be either linear or branched.

The method for producing the compound represented by formula (1) is not particularly limited. For example, rosin, which is a mixture of resin acids such as abietic acid, neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and levopimaric acid, is added with an alkylene oxide by a conventional method. A method of producing a rosin polyoxyalkylene adduct represented by the general formula (1) by addition, or adding an alkylene oxide to R ² in advance by a conventional method using a catalyst or the like, and then rosin and an ester and a method of producing a rosin polyoxyalkylene adduct represented by the general formula (1) by converting the rosin polyoxyalkylene adduct.

The compound represented by the general formula (1) is preferably added at a rate of 0.00001 to 1% by mass, and a rate of 0.00005 to 0.4% by mass, based on the total amount of Portland cement and silica fume. It is more preferable to be added at a rate of 0.0001 to 0.1% by mass.

(1-2) Portland cement (binder):
The cement composition of the present invention contains Portland cement as a binder. By blending Portland cement as an essential component, the Portland cement exhibits hydraulic properties due to a chemical reaction when mixed with water.

Examples of such Portland cement include ordinary Portland cement, high-early-strength Portland cement, ultra-early-strength Portland cement, moderate-heat Portland cement, low-heat Portland cement, sulfate-resistant Portland cement, and the like. Among these, moderate heat Portland cement and low heat Portland cement are preferred, and low heat Portland cement is more preferred, from the viewpoint of reducing the viscosity of the cement composition and reducing temperature cracking of the cement composition.

As the binder, Portland cement may be used alone, and Portland cement may be used in combination with a pozzolanic substance or a fine powder admixture having latent hydraulicity as long as the effect of the present invention is not impaired. Examples of the fine powder admixture include fine powder of blast furnace slag, fly ash, and fine powder of limestone. Additionally, the binder may include expansive materials, gypsum, and the like.

(1-3) Silica fume:
The cement composition of the present invention contains silica fume. Incorporation of silica fume results in low viscosity despite a low water binder ratio (ie, a small amount of water used). Furthermore, a cement composition having high strength or ultra-high strength after hardening can be obtained.

Silica fume may be added separately to a binder containing Portland cement or the like, or may be used as premixed in cement such as Portland cement (premixed silica fume (silica fume premixed cement)).

Silica fume premix cement includes, for example, silica fume cement (SFC) (manufactured by Ube-Mitsubishi Cement Co., Ltd.), silica fume premix cement (SFPC) (manufactured by Taiheiyo Cement Co., Ltd.), and the like. Further, another silica fume may be added to these silica fume premixed cements.

Silica fume is usually used in an amount of 1 to 50 parts by weight per 100 parts by weight of Portland cement. In the silica fume premixed cement, about 5 to 25 parts by mass can be blended with 100 parts by mass of various Portland cements.

(1-4) dispersant:
The cement composition of the present invention contains a dispersant. By containing this dispersant, even a cement composition with a high proportion of powder has an effect that it becomes moderately viscous and can be handled.

Examples of such dispersants include ligninsulfonic acid-based dispersants, naphthalenesulfonic acid-based dispersants, polycarboxylic acid-based dispersants, and aminosulfonic acid-based dispersants. A polycarboxylic acid-based dispersant is preferred in order to sufficiently lower the viscosity of a high-strength or ultra-high-strength cement composition.

As such a polycarboxylic acid-based dispersant, a known one or a commercially available one can be used. For example, known ones include those shown in JP-A-2009-263181, etc., and commercially available ones are Tupole SSP-104 (manufactured by Takemoto Yushi Co., Ltd.) and Master Glenium SP8HU (manufactured by BASF). , Mighty 3000T (manufactured by Kao Corporation), and Flolic SF500U (manufactured by Floric Corporation).

The dispersant is preferably added as an active ingredient at a rate of 0.01 to 3.0% by mass, more preferably 0.10 to 2.0% by mass, based on the total amount of Portland cement and silica fume. more preferably.

(1-5) Defoamer:
The cement composition of the present invention contains an antifoaming agent. By containing an antifoaming agent, it is possible to reduce the amount of air mixed into the cement composition, thereby obtaining a stronger cement composition.

Examples of such antifoaming agents include ester antifoaming agents, polyether antifoaming agents, mineral oil antifoaming agents, and powder antifoaming agents. A polyether-based antifoaming agent is preferable in order to ensure sufficient antifoaming properties with a small amount. Examples of such polyether antifoaming agents include those obtained by adding alkylene oxide to substances having active hydrogen such as various alcohols and amines.

The antifoaming agent is preferably added in a proportion of 0.0001 to 0.1% by mass, more preferably in a proportion of 0.0005 to 0.05% by mass, based on the total amount of Portland cement and silica fume. is more preferred.

(1-6) Water:
The cement composition of the present invention contains water. By containing water, the cement composition hardens and develops strength.

Water is preferably added at a rate of 5 to 30% by mass, more preferably at a rate of 8 to 25% by mass, and more preferably at a rate of 8 to 20% by mass, based on the total amount of Portland cement and silica fume. It is more preferable to add in proportion.

(1-7) Other components:
The cement composition according to the present invention can be used in combination with existing admixtures and admixtures as long as it does not increase the viscosity and affect the air content. Such admixtures include ground granulated blast furnace slag, fly ash, limestone fine powder, expansive agents, etc. Admixtures include AE water reducing agents, high performance AE water reducing agents, high performance water reducing agents, AE agents, and shrinkage reduction. agents, thickeners, setting retarders, curing accelerators and the like.

In addition, fine aggregate and coarse aggregate are exemplified as the aggregate when the aggregate is used for the preparation of the cement composition according to the present invention. Examples of fine aggregate include river sand, mountain sand, sea sand, crushed sand, slag fine aggregate, and the like. Examples of coarse aggregate include river gravel, crushed stone, and lightweight aggregate.

Furthermore, the water binder ratio of the cement composition according to the present invention is 0.05 to 0.30, 0.08 to 0.25 in order to obtain high strength or ultra high strength after hardening. is preferred , and 0.08 to 0.20 is more preferred.

Examples will be given below in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to these examples. In the following examples and comparative examples, "parts" means parts by weight and "%" means % by weight, unless otherwise specified.

Test category 1 (synthesis of compound represented by general formula (1))
- Synthesis of compound (A-1):
626.9 g of "gum rosin" X grade (acid value: 171 mg KOH/g) from the People's Republic of China (hereinafter simply referred to as "made in China") and 2.0 g of potassium hydroxide are placed in a 2 L stainless steel pressure container. was charged, heated to 120° C., and dehydrated under reduced pressure for 1 hour while stirring. After returning to normal pressure with nitrogen, 1264 g of ethylene oxide was injected under the conditions of 0.6 MPa at 150 to 160° C., then 107 g of propylene oxide was injected under the same conditions, and aging was performed at that temperature for 1 hour. . Then, it was cooled, 20 g of an adsorbent (trade name: Kyoward 600 manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after dehydration under reduced pressure at 120 ° C., pressure filtration was performed to obtain a compound (A-1). .

・ Synthesis of compound (A-2) In a 2 L stainless steel pressure vessel, 541.7 g of X grade (acid value: 171 mg KOH / g) of “gum rosin” from China and 2.0 g of potassium hydroxide were charged, and 120 The mixture was heated to °C and dehydrated under reduced pressure for 1 hour while stirring. After returning to normal pressure with nitrogen, 1456 g of ethylene oxide was injected under the condition of 0.4 MPa at 150 to 160° C., and aging was performed for 1 hour at that temperature. After cooling, 2.7 g of 85% phosphoric acid was added, and after dehydration under reduced pressure at 120° C., filtration under pressure was carried out to obtain compound (A-2).

Synthesis of compound (A-3) In a 1 L glass reaction vessel, 500.0 g of the reagent α-methoxy-ω-hydroxy-poly(m = 45) oxyethylene and X grade (acid value : 171 mg KOH/g) and 7.2 g of methanesulfonic acid were charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound (A-3).

Synthesis of compound (A-4) In a 1 L glass reaction vessel, 500.0 g of α-methallyl-ω-hydroxy-poly(m = 50) oxyethylene and X grade of Chinese “gum rosin” (acid value: 171 mg KOH) were added. /g) and 12.7 g of p-toluenesulfonic acid monohydrate were charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound (A-4).

Synthesis of compound (A-5) In a 1 L glass reaction vessel, 600.0 g of polyoxyethylene glycerol ether (an average of 30 mol of ethylene oxide added to glycerin) and X grade of Chinese "gum rosin" (acid value: 278.7 g of 171 mg KOH/g) and 8.2 g of methanesulfonic acid were charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound (A-5).

- Synthesis of compound (A-6) In a 1 L glass reaction vessel, 400.0 g of poly(m = 22) ethylene glycol and 262.5 g of X grade (acid value: 171 mg KOH / g) of "gum rosin" produced in China, 15.4 g of p-toluenesulfonic acid monohydrate was charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate reached 99% or more, the reaction was terminated and purified to obtain compound (A-6).

・ Synthesis of compound (A-7) In a 2 L stainless steel pressure vessel, 626.9 g of X grade (acid value: 171 mg KOH / g) of Chinese “gum rosin” and 1.2 g of potassium hydroxide were charged, and 120 The mixture was heated to °C and dehydrated under reduced pressure for 1 hour while stirring. After returning to normal pressure with nitrogen, 264 g of ethylene oxide and 349 g of propylene oxide were mixed at 150 to 160° C., injected under pressure of 0.5 MPa, and aged at that temperature for 1 hour. After that, it was cooled, 12 g of an adsorbent (trade name: Kyoward 600 manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and after dehydration under reduced pressure at 120 ° C., pressure filtration was performed to obtain a compound (A-7). .

・Synthesis of compound (A-8) α-methallyl-ω-hydroxy-poly(m=50) oxyethylene was changed to α-methallyl-ω-hydroxy-poly(m=90) oxyethylene, and the charge ratio of gum rosin was Compound (A-8) was obtained in the same manner as for compound (A-4) except that

Table 1 summarizes the contents of the compounds (A-1) to (A-8) and (R-1) to (R-2) synthesized above. As compounds (R-1) and (R-2), commercially available products described later were used.

P-1 to P-2 in Table 1 are described below.
R-1: X grade of Chinese "gum rosin" R-2: Reagent polyethylene glycol (molecular weight 1000)

R ¹ and AO in Table 1 are described below.
Gum rosin acyl residue: Gum rosin carboxylic acid with hydroxyl group removed Gum rosin acyl residue: H = 2:1; Gum rosin carboxylic acid with hydroxyl group removed: hydrogen atom = 2:1 (molar ratio)
EO: oxyethylene group PO: oxypropylene group

Test category 2 (preparation of mortar as cement composition)
(Examples 1 to 10, Comparative Examples 1 to 3)
Using a high-power mixer (trade name “CB-34” manufactured by Maruto Seisakusho Co., Ltd.), a binder, a polycarboxylic acid-based dispersant having a solid content concentration of 25%, and a polyether are mixed with the contents described in Tables 2 and 3. A mortar was prepared by adding a system antifoaming agent ((name of product name) “AFK-2” manufactured by Takemoto Oil & Fat Co., Ltd.) to fine aggregates and each compound prepared in test section 1 in order, and kneading for 480 seconds. A target mortar flow value was set to 270±10 mm. In Table 3, "compound" indicates a compound represented by general formula (1).

The “polycarboxylic acid-based dispersant having a solid content concentration of 25%” was prepared as follows (Example 1 of JP-A-2009-263181 (see paragraph 0024)). That is, 1687 g of distilled water, 174 g (1.5 mol) of maleic acid and 1513 g (1.0 mol) of α-allyl-ω-hydroxy-poly(oxyethylene unit number is 33) oxyethylene were charged into a reactor and stirred. After uniformly dissolving while stirring, the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 70° C. in a warm water bath, and an aqueous solution prepared by dissolving 25 g of sodium persulfate in 100 g of distilled water was added to initiate a radical copolymerization reaction. After 1 hour, an aqueous solution prepared by dissolving 25 g of sodium persulfate in 100 g of distilled water was added, and the mixture was kept at 70° C. for 3 hours to carry out a radical copolymerization reaction. The reaction system was adjusted to a solid content concentration of 25% with distilled water to prepare a "polycarboxylic acid-based dispersant having a solid content concentration of 25%".

The binders and fine aggregates in Table 2 are described below.
Binder: Silica fume premixed cement (manufactured by Ube-Mitsubishi Cement Co., Ltd., trade name “Silica fume cement”). "Silica fume premixed cement" is cement obtained by adding fine particles of silica fume to low-heat Portland cement.
Fine aggregate: Land sand from the Oi River water system

Test category 3 (physical property evaluation of mortar (cement composition))
The air content, mortar flow value, flow time, and compressive strength of each mortar prepared in test section 2 were measured as follows, and the results are summarized in Table 3.

・Amount of air (% by volume):
For the mortar immediately after kneading, a 400 ml metal cylindrical container was used, and the unit volume mass was determined according to Japanese Industrial Standards JIS A 1116-5, and calculated according to Japanese Industrial Standards JIS A 1116-5.
・Mortar flow value (mm):
The mortar immediately after kneading was measured according to Japanese Industrial Standard JIS R 5201.
・Descent time (seconds):
It was measured using a _J14 funnel in accordance with the filling mortar fluidity test method (Japan Society of Civil Engineers standard JSCE-F 541).
・Compressive strength:
Compressive strength at 28 days of age was measured according to Japanese Industrial Standards JIS-A1108. Specifically, a tin mold with a diameter of 50 mm × 100 mm is filled with mortar after measuring the mortar flow value and the flow time, and is placed in a constant temperature room at a temperature of 20 ° C and a humidity of 80% until the material age reaches 24 hours. nurtured. After that, it was removed from the mold and cured in water at 20° C. until it reached a material age of 28 days. Then, after finishing the surface by polishing, the compressive strength was measured.
・The addition rate is the mass% of each dispersant, antifoaming agent, and compound represented by general formula (1) with respect to silica fume premixed cement (composed of Portland cement and silica fume) as a binder. showed that.

(result)
As is clear from the results shown in Examples 1 to 10 and Comparative Examples 1 to 3 in Table 3, the cement compositions of the present invention have higher viscosity than conventional cement compositions (Comparative Examples 1 to 3). lower, while the air volume remains unchanged. It was also confirmed that a high compressive strength is maintained and that a high-strength or ultra-high-strength cement composition can be formed.

The cement composition of the present invention can be used as a high-strength or ultra-high-strength cement composition for civil engineering and construction.

Claims (15)

A compound represented by the following general formula (1) obtained by adding an alkylene oxide to the resin acid of rosin, which is a mixture of resin acids, Portland cement, silica fume, water, a dispersant and an antifoaming agent,
A cement composition having a water binder ratio of 0.05 to 0.30 .

(However, in general formula (1), R ¹ represents an acyl residue of resin acid contained in rosin or a hydrogen atom (provided that when n is 1, R ¹ represents an acyl residue of resin acid contained in rosin. and when n is 2 or more, at least one of ^R1 is an acyl residue of a resin acid contained in rosin), ^R2 is a hydrogen atom, an acyl residue of a resin acid contained in rosin group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 3 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or 2 to 2 carbon atoms 20 polyvalent carboxylic acid acyl residue (however, when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom); represents an oxyalkylene group, m is a number of 1 to 200, n is a number of 1 to 20, and the above m and n are numbers satisfying the relationship m × n = 1 to 200 and 50 mol% or more of AO having 2 or 3 carbon atoms is an oxyalkylene group.) The cement composition according to claim 1, wherein said AO in said general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms. The cement composition according to claim 1 or 2, wherein ^R1 in the general formula (1) is an acyl residue of natural rosin. The cement composition according to any one of claims 1 to 3, wherein 90 mol% or more of the AO in the general formula (1) contains oxyalkylene groups having 2 to 3 carbon atoms. Any one of claims 1 to 4, wherein the n in the general formula (1) is a number from 1 to 6, and the m and n are numbers satisfying the relationship m × n = 1 to 100 or the cement composition according to claim 1. R ² in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a polyhydric alcohol having 3 to 6 carbon atoms, or a hydroxyl group. (provided that when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom), the cement according to any one of claims 1 to 5 Composition. The cement composition according to any one of claims 1 to 6, wherein R ¹ in the general formula (1) is an acyl residue of gum rosin. The cement composition according to any one of claims 1 to 7, wherein 50 mol% or more of the AO in the general formula (1) is an oxyalkylene group having 2 carbon atoms. Any one of claims 1 to 8, wherein the n in the general formula (1) is a number from 1 to 3, and the m and n are numbers satisfying the relationship m × n = 5 to 60 or the cement composition according to claim 1. R ² in the general formula (1) is a hydrogen atom, an acyl residue of gum rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a hydroxyl group from a polyhydric alcohol having 3 to 6 carbon atoms. (provided that when at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom), the cement according to any one of claims 1 to 9 Composition. The compound represented by the general formula (1) is contained in a proportion of 0.00001 to 1 part by mass per 100 parts by mass of Portland cement and silica fume, according to any one of claims 1 to 10. cement composition. Any one of claims 1 to 10, wherein the compound represented by the general formula (1) is contained in a proportion of 0.00005 to 0.4 parts by mass per 100 parts by mass of Portland cement and silica fume. The cement composition according to . Any one of claims 1 to 10, wherein the compound represented by the general formula (1) is contained in a proportion of 0.0001 to 0.1 parts by mass per 100 parts by mass of Portland cement and silica fume. The cement composition according to . The cement composition according to any one of claims 1 to 13, wherein the dispersant is a polycarboxylic acid-based dispersant. A cement composition according to any one of claims 1 to 14, wherein said antifoaming agent is a polyether antifoaming agent.