WO2019189922A1

WO2019189922A1 - Antifoam composition and admixture for hydraulic composition including same

Info

Publication number: WO2019189922A1
Application number: PCT/JP2019/014400
Authority: WO
Inventors: 岡田朋久; 對馬大郎
Original assignee: 東邦化学工業株式会社
Priority date: 2018-03-30
Filing date: 2019-03-30
Publication date: 2019-10-03
Also published as: JPWO2019189922A1; JP7267997B2; CN111936446A

Abstract

[Problem] To provide: an antifoam composition which achieves both an antifoaming property and compatibility in an admixture for a hydraulic composition; and an admixture for a hydraulic composition with which concrete having less coarse bubble marks on the surface thereof and an excellent surface appearance can be produced. [Solution] This antifoam composition includes: a polyoxyalkylene compound (A); and a phosphoric acid ester compound (B) represented by general formula (3) (where R⁶ represents an alkyl group having 1-30 carbon atoms, an alkenyl group having 2-30 carbon atoms, or an aryl group having 6-30 carbon atoms, and A⁴O represents an oxyalkylene group having 2-4 carbon atoms, p represents an integer of 0 or 1-50, q represents an integer of 1-3, and M represents a hydrogen atom, an alkaline metal atom, a Group 2 metal atom, an ammonium group, or an organic ammonium group).

Description

Antifoam composition and admixture for hydraulic composition containing the same

The present invention relates to an antifoaming agent composition and an admixture for a hydraulic composition containing the same.

[To date, various cement admixtures have been used to improve the quality of concrete. Among them, AE agent (air-entraining agent) and AE water-reducing agent increase the fluidity of uncured concrete by entraining air bubbles in the concrete, and improve the workability during construction and the frost damage resistance of the hardened concrete It is often used in. However, if the amount of air entrained in the concrete increases, coarse bubbles are likely to be generated, which causes uneven filling and consequently reduced strength of the cured body, and also causes voids (bubble marks) on the surface of the cured body and impairs the appearance. It becomes.

Against this background, concrete admixtures are generally used in combination with concrete defoamers, and are transported to ready-mix factories in the form of products that contain antifoams. Often stored in tanks. For example, Patent Documents 1 and 2 disclose concrete admixtures containing a polyoxyalkylene fatty acid ester having a specific structure as an antifoam component.

JP-A-61-111950 Japanese Patent Laid-Open No. 1-51353

However, defoaming agents for concrete have a hydrophobic portion in their chemical structure, so they are easy to separate in water, especially when stored in an admixture tank that does not have a stirring facility. Appears prominently over time. When admixtures are used in a state where the antifoam component is separated in the product, in the fresh property confirmation test of concrete, it has been confirmed that the air amount varies and the air amount cannot be managed accurately. Although the compatibility in concrete admixture is improved by increasing the hydrophilicity of the antifoaming agent, the defoaming property of coarse bubbles will be reduced, and both the antifoaming property and the compatibility in the admixture will be compatible. There is a need for defoamers for concrete.

The object of the present invention is to produce an antifoaming agent that has both antifoaming properties and compatibility in the admixture for hydraulic composition, and concrete that has few coarse bubble marks on the concrete surface and excellent surface aesthetics. It is to provide an admixture for a hydraulic composition.

As a result of investigations by the present inventors, an antifoaming agent that achieves both antifoaming properties and compatibility in an admixture for a hydraulic composition by using a specific phosphate compound in combination with an antifoaming agent. As a result, the present invention was completed.
That is, this invention relates to the antifoamer composition as described in the following [1] thru | or [4], and the admixture for hydraulic compositions as described in [5].

[1] The following general formula (1):
R ¹ O— (A ¹ O) _n1 —R ² (1)
(Where
R ¹ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an acyl group having 2 to 30 carbon atoms,
R ² represents a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms,
n1 represents an integer of 6 to 100. )
Or the following general formula (2):
R ⁴ O— (A ² O) _n2 —R ³ O— (A ³ O) _n3 —R ⁵ (2)
(Where
R ³ represents a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A ² O and A ³ O each independently represents an oxyalkylene group having 2 to 4 carbon atoms,
n2 and n3 represent 0 or a positive integer whose sum is an integer of 6 to 100. )
A polyoxyalkylene compound (A) represented by:
The following general formula (3):

(Where
R ⁶ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms,
p represents 0 or an integer of 1 to 50;
q represents an integer of 1 to 3,
M represents a hydrogen atom, an alkali metal atom, a Group 2 metal atom, an ammonium group, or an organic ammonium group. )
The antifoamer composition containing the phosphate compound (B) shown by these.

[2] The defoamer composition according to [1], wherein the mass ratio (A) / (B) of the polyoxyalkylene compound (A) and the phosphate ester compound (B) is 99/1 to 60/40. object.

[3] Furthermore, the following general formula (4):
R ⁷ O— (A ⁵ O) _m —H (4)
(Where
R ⁷ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms,
A ⁵ O represents an oxyalkylene group having 2 to 3 carbon atoms,
m represents an integer of 1 to 5. )
The antifoamer composition as described in [1] or [2] containing the glycol ether (C) which has a structure represented by these.

[4] The polyoxyalkylene compound (A) represented by the general formula (1) is represented by the following general formula (5):
R ^{1 '} O- (EO) _k -R ² ' (5)
(Where
R ¹ ′ represents an unsaturated fatty acid residue having 12 to 30 carbon atoms,
R ² ′ represents a hydrogen atom or an unsaturated fatty acid residue having 12 to 30 carbon atoms,
EO represents an oxyethylene group,
k represents an integer of 6 to 100. )
The antifoamer composition according to any one of [1] to [3], comprising a polyoxyalkylene compound (A ′) represented by the formula:

[5] A hydraulic composition admixture comprising the antifoam composition according to any one of [1] to [4].

The antifoaming composition of the present invention is excellent in antifoaming properties and compatibility in the admixture for hydraulic composition. Further, by using the admixture for hydraulic composition containing the antifoam composition of the present invention, there are few coarse bubble marks on the concrete surface without impairing the fresh properties and strength development, and the surface appearance is excellent. Concrete can be made.

Hereinafter, the antifoaming composition of the present invention will be described in detail.
The antifoaming agent composition of the present invention comprises a polyoxyalkylene compound (A) represented by the following general formula (1) or general formula (2), and a phosphoric acid ester compound represented by the following general formula (3) ( And B).

<Polyoxyalkylene compound (A)>
The polyoxyalkylene compound (A) constituting the antifoam composition of the present invention is one or a mixture of two or more selected from compounds represented by the following general formula (1) and general formula (2). .
R ¹ O— (A ¹ O) _n1 —R ² (1)
(Where
R ¹ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an acyl group having 2 to 30 carbon atoms,
R ² represents a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms,
n1 represents an integer of 6 to 100. )

R ⁴ O— (A ² O) _n2 —R ³ O— (A ³ O) _n3 —R ⁵ (2)
(Where
R ³ represents a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A ² O and A ³ O each independently represents an oxyalkylene group having 2 to 4 carbon atoms,
n2 and n3 represent 0 or a positive integer whose sum is an integer of 6 to 100. )

Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group, tetradecyl group (milstil group), pentadecyl group, hexadecyl group (Palmityl group), octadecyl group (stearyl group), icosyl group, docosyl group (behenyl group), tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group and the like. Among these, from the viewpoint of the defoaming effect, an alkyl group having 8 to 24 carbon atoms is preferable, and an alkyl group having 12 to 22 carbon atoms is more preferable.

Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group and 1-hexenyl. Group, 2-hexenyl group, 1-octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, eicosenyl group, dococenyl group, tetracosenyl group These may have a branched structure or a cyclic structure. Among these, from the viewpoint of the defoaming effect, an alkenyl group having 8 to 24 carbon atoms is preferable, and an alkenyl group having 12 to 22 carbon atoms is more preferable.

The acyl group having 2 to 30 carbon atoms is preferably a saturated or unsaturated fatty acid residue having 8 to 30 carbon atoms, such as 2-ethylhexanoic acid residue, capric acid residue, lauric acid residue, Examples include myristic acid residue, palmitic acid residue, stearic acid residue, behenic acid residue, isopalmitic acid residue, isostearic acid residue, oleic acid residue, linoleic acid residue, linolenic acid residue and the like. Among these, from the viewpoint of the defoaming effect, an acyl group having 8 to 24 carbon atoms is preferable, and an acyl group having 12 to 22 carbon atoms is more preferable.

Examples of the divalent hydrocarbon group having 1 to 30 carbon atoms include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene. Group, 1,4-butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group, etc. A linear or branched alkylene group having 1 to 20 carbon atoms; cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, methylene-trimethylcyclohexyl group, bicyclohexylene group, bicyclo [2 2.1] C3-C20 cycloalkylene group such as heptane-2,6-diyl group; 1,4-dimethylenecyclo Alkylene, cycloalkylene-alkylene groups having 5 to 14 carbon atoms such as lanthanum group, 1,4-diethylenecyclopentane group, 1,4-dimethylenecyclohexane group, 1,4-diethylenecyclohexane group; phenylene group, tolylene group , Arylene groups having 6 to 20 carbon atoms such as dimethylphenylene group, naphthylene group, biphenylene group, anthrylene group, and trimethylphenylene group.

A ¹ O, A ² O and A ³ O are oxyalkylene groups having 2 to 4 carbon atoms, specifically, oxyethylene group, 1,2- or 1,3-oxypropylene group, 1,2- 1,3- or 1,4-oxybutylene group, among which oxyethylene group and 1,2-oxypropylene group are preferable.

n1 is the number of added moles of alkylene oxide, and is an integer of 6 to 100, but is preferably an integer of 10 to 50 in view of the defoaming effect. When n1 is 2 or more, n1 A ¹ Os may be the same or different, and in the case of being different,-(A ¹ O) _n1- may be any addition type of random addition, block addition, or alternate addition. Among these, from the viewpoint of the defoaming effect, the added mole number of ethylene oxide is preferably 2 to 15, more preferably 5 to 10, and preferably the added mole number of propylene oxide is 10 to 70, 20 to 40 is more preferable.

N2 and n3 are the number of added moles of alkylene oxide, and the total is an integer of 6 to 100, and 0 or a positive integer which is preferably an integer of 10 to 50 in view of the defoaming effect. When the total of n2 and n3 is 2 or more, the types of alkylene oxides may be the same or different, and when they are different, any addition form of random addition, block addition or alternating addition may be used. Among these, from the viewpoint of the defoaming effect, the total number of moles of ethylene oxide added is preferably 2 to 15, more preferably 5 to 10, and the total number of moles added of propylene oxide is 10 to 70. Preferably, 20 to 40 is more preferable.

The polyoxyalkylene compound (A) is particularly preferably a compound having a polyoxyethylene block and a polyoxypropylene block represented by the following general formula (1a) from the viewpoint of the defoaming effect.
R ¹ O— (EO) _n4 — (PO) _n5 —R ² (1a)
(Wherein R ¹ and R ² represent the same as those in formula (1),
EO represents an oxyethylene group, PO represents an oxypropylene group,
n4 represents an integer of 2 to 15, preferably an integer of 5 to 10,
n5 represents an integer of 10 to 70, preferably an integer of 20 to 40. )

The content of the polyoxyalkylene compound (A) in the antifoaming agent composition of the present invention is preferably 60 to 99% by mass, more preferably 70 to 97% by mass, and particularly preferably 80 from the viewpoint of the defoaming effect. To 95% by mass.

The antifoaming agent composition of the present invention contains 1 to 15 polyoxyalkylene compounds (A ′) represented by the following general formula (1b) from the viewpoint of improving the compatibility in the admixture for hydraulic compositions. It is preferable to contain 2% by mass, and more preferably 2 to 10% by mass.
R ^{1 '} O- (EO) _k -R ² ' (1b)
(Wherein R ¹ ′ represents an unsaturated fatty acid residue having 12 to 30 carbon atoms,
R ² ′ represents a hydrogen atom or an unsaturated fatty acid residue having 12 to 30 carbon atoms,
EO represents an oxyethylene group,
k represents an integer of 6 to 100, preferably an integer of 7 to 20. )
Examples of the unsaturated fatty acid residue having 12 to 30 carbon atoms include oleic acid residue, linoleic acid residue, linolenic acid residue and the like.

<Phosphate ester compound (B)>
The phosphoric acid ester compound (B) constituting the antifoam composition of the present invention has a structure represented by the following general formula (3), a phosphoric acid monoester and a salt thereof, a phosphoric acid diester and a salt thereof, and 1 type of compound chosen from phosphoric acid triester, or 2 or more types of mixtures is included.

(Where
R ⁶ represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms,
p represents 0 or an integer of 1 to 50;
q represents an integer of 1 to 3,
M represents a hydrogen atom, an alkali metal atom, a Group 2 metal atom, an ammonium group, or an organic ammonium group. )

In the above formula, specific examples of the alkyl group having 1 to 30 carbon atoms and the alkenyl group having 2 to 30 carbon atoms in R ³ include the groups exemplified as those in the general formula (1). However, from the viewpoint of improving compatibility, an alkyl group having 1 to 12 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.

Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, naphthyl group and other unsubstituted aryl groups, alkyl groups, alkoxy groups, aralkyl groups, etc. The said aryl group which has a substituent is mentioned.

In the above formula, p is the added mole number of the oxyalkylene group and represents 0 or an integer of 1 to 50. Among these, from the viewpoint of improving the compatibility, n is preferably 1 to 30, more preferably 2 to 20, and particularly preferably 2 to 10.

In the above formula, p represents an integer of 1 to 3, that is, the compound represented by the formula (3) is a phosphoric acid monoester and a salt thereof when p is 1, and a phosphoric diester and a salt when p is 2. When p is 3, it is a phosphoric acid triester.
The ratio of the phosphoric acid monoester and its salt / phosphoric diester and its salt / phosphoric triester and its salt in the total amount of the compound represented by the formula (3) is determined from the viewpoint of the effect of improving the compatibility. And the salt thereof is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, the phosphoric diester and the salt thereof are preferably 20 to 80% by mass, and 30 to 70% by mass. More preferably, the phosphoric acid triester and the salt thereof are preferably 0 to 10% by mass, and more preferably 0 to 5% by mass.

In the formula, M is a hydrogen atom, an alkali metal, a Group 2 metal, an ammonium group, or an organic ammonium group. Examples of the alkali metal include lithium (Li), sodium (Na), and potassium (K). Examples of the Group 2 metal include beryllium (Be), magnesium (Mg), calcium (Ca), Examples include strontium (Sr) and barium (Ba). The organic ammonium group is an ammonium group derived from an organic amine. Examples of the organic amine include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, methylamine, dimethylamine, triethylamine, ethylamine, diethylamine, and triethylamine. Etc. Among these, hydrogen atoms are preferable because coarse bubbles are less likely to be generated.

The content of the phosphate ester compound (B) in the antifoam composition of the present invention is preferably 1 to 40% by mass from the viewpoint of the compatibility improving effect in the admixture for hydraulic composition. More preferably, it is 2 to 20% by mass, particularly preferably 3 to 10% by mass.
Further, the mass ratio (A) / (B) of the polyoxyalkylene compound (A) and the phosphate ester compound (B) is preferably 99/1 to 60/40, more preferably from the viewpoint of the effect of improving compatibility. 98/2 to 80/20, more preferably 97/3 to 90/10.

<Glycol ether (C)>
The antifoam composition of the present invention preferably further contains a glycol ether (C) represented by the following general formula (4) from the viewpoint of improving the compatibility in the admixture for hydraulic composition. .
R ⁷ O— (A ⁵ O) _m —H (4)
(Where
R ⁷ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms,
A ⁵ O represents an oxyalkylene group having 2 to 3 carbon atoms,
m represents an integer of 1 to 5. )

Examples of the glycol ether (C) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, tetra Examples include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, and mixtures of two or more thereof.

The content of the glycol ether (C) in the antifoam composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from the viewpoint of the compatibility improving effect in the admixture for hydraulic composition. Is 1 to 10% by mass, particularly preferably 2 to 6% by mass.

Examples of components that can be optionally added during preparation of the antifoam composition of the present invention include known and publicly used surfactants, thickeners, preservatives, antifoaming agents, and the like, and these can also be appropriately blended. The blending ratio of these components can be appropriately determined according to the type of the selected component and the purpose of use. Moreover, you may dilute the antifoamer composition of this invention with water or an aqueous solvent as needed.

The antifoaming composition of the present invention can be used in the form of an admixture for a hydraulic composition in which known and publicly used additives for hydraulic compositions are appropriately adopted and combined. Specifically, conventionally known cement dispersant, water reducing agent, high performance water reducing agent, AE agent, AE water reducing agent, high performance AE water reducing agent, foaming agent, antifoaming agent, setting retarder, setting accelerator, separation At least one other additive selected from the group consisting of a reducing agent, a thickening agent, a shrinkage reducing agent, a curing agent, a water repellent and the like can be blended.
The content of the antifoam composition of the present invention in the admixture for hydraulic composition is preferably 0.03 to 0.2% by mass.
In addition, in this specification, a hydraulic composition refers to the composition containing the powder (hydraulic powder) which has a physical property hardened | cured by a hydration reaction, for example, cement, gypsum, fly ash, etc. Moreover, when hydraulic powder is a cement, a hydraulic composition is also called a cement composition.

Generally, cement dispersants are appropriately combined and used according to concrete production conditions and performance requirements. The same applies to the cement dispersant of the present invention, which is used as a cement dispersant alone or as a main agent, but as a modification aid for a cement dispersant having a large slump loss, or has an initial water reduction. It can be used in combination as a high cement dispersant.

Known cement dispersants include salts of polycarboxylic acid copolymers described in Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, and the like, and naphthalenesulfonic acid formalin condensates. And salts of melamine sulfonic acid formalin condensate, lignin sulfonate, sodium gluconate and sugar alcohol.

Specific examples of the AE agent include an anionic AE agent, a nonionic AE agent, and an amphoteric AE agent.
Examples of the setting retarder include inorganic setting retarders and organic setting retarders.
Examples of the accelerator include inorganic accelerators and organic accelerators.
Examples of thickeners / separation reducing agents include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymers, nonionic thickeners, and the like.
Examples of antifoaming agents include nonionic antifoaming agents, silicone antifoaming agents, higher alcohols, and mixtures containing these as main components.

When the admixture for hydraulic composition of the present invention is applied to, for example, a cement composition, the component constituting the cement composition is a conventionally used component for concrete, and cement (for example, ordinary Portland cement, early strength) Portland cement, ultra-high strength Portland cement, low heat / moderate heat Portland cement or blast furnace cement, etc.), aggregate (ie fine aggregate and coarse aggregate), admixture (eg silica fume, calcium carbonate powder, blast furnace slag fine powder, fly Ash, etc.), expansion material and water.

The antifoam composition of the present invention includes various anti-foaming agents for paints, pulp production process, paper making process, wastewater treatment process, building material paper making process, fermentation process, photosensitive resin development process and polymer polymerization process. Also suitable for use as an antifoaming agent.

Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples and comparative examples. Unless otherwise specified,% represents mass%.

Production Example 1
A stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen introduction tube was charged with 202 g of stearyl alcohol and 4 g of 96% potassium hydroxide, the inside of the reaction vessel was purged with nitrogen, and the temperature was increased to 150 ° C. under a nitrogen atmosphere. Heated. While maintaining 150 ° C. under safe pressure, 198 g of ethylene oxide was introduced into the reactor in 5 hours, and the temperature was maintained for 1 hour. Thereafter, it is cooled to 120 ° C., and 1088 g of propylene oxide is introduced into the reactor in 10 hours while maintaining at 120 ° C. under a safe pressure, and the temperature is maintained for 4 hours to complete the alkylene oxide addition reaction. 1492 g (A1 compound) of polyoxypropylene glycol monostearyl ether was obtained.

Production Example 2
A stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet tube was charged with 200 g of 1-tridecanol and 2.8 g of 96% potassium hydroxide, the inside of the reaction vessel was purged with nitrogen, and the nitrogen atmosphere was maintained. Heated to 150 ° C. Then, 182 g of ethylene oxide was introduced into the reactor in 2 hours while maintaining 150 ° C. under a safe pressure, and the temperature was maintained for 1 hour. Then, it cooled to 120 degreeC, 1177g of propylene oxide was introduce | transduced in the reactor in 10 hours, hold | maintaining at 120 degreeC under safe pressure, and the temperature was hold | maintained for 4 hours. Then, it heated again to 150 degreeC, 200 g of ethylene oxide was introduce | transduced in the reactor in 2 hours, hold | maintaining 150 degreeC under safe pressure, the temperature was maintained for 1 hour, and the alkylene oxide addition reaction was completed. The obtained compound (1762 g) was charged with 220 g of 65% stearic acid and 0.6 g of sodium hypophosphite, and heated to 220 ° C. in a nitrogen atmosphere. The esterification reaction was carried out at 225 ° C. for 18 hours until the acid value became 2.0 or less to obtain 1983 g (A2 compound) of 1-tridecanol polyoxyethylene / polyoxypropylene ether stearate.

Production Example 3
A stainless steel high-pressure reactor equipped with a thermometer, a stirrer, a pressure gauge, and a nitrogen introduction tube was charged with 216 g of oleic acid and 0.2 g of 96% potassium hydroxide, the inside of the reaction vessel was purged with nitrogen, and 170 under a nitrogen atmosphere. Heated to ° C. And 270g of ethylene oxide was introduce | transduced in the reactor in 5 hours, keeping 170 degreeC under safety pressure, and the temperature was hold | maintained after that for 1 hour, and 486g (A3 compound) of polyethylene glycol oleate was obtained.

Production Example 4
A stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen introduction tube was charged with 77 g of methanol and 1.2 g of 96% potassium hydroxide, the inside of the reaction vessel was purged with nitrogen, and 120 ° C. under a nitrogen atmosphere. Until heated. Then, 708 g of propylene oxide was introduced into the reactor in 10 hours while maintaining 120 ° C. under a safe pressure, and the temperature was maintained for 2 hours. Thereafter, the mixture was heated to 150 ° C., and 216 g of ethylene oxide was introduced into the reactor in 5 hours while maintaining 150 ° C. under a safe pressure, and the alkylene oxide addition reaction was completed by maintaining the temperature for 1 hour. 1002 g of ether was obtained. Thereafter, the reaction vessel was set to 40 ° C., and 88.5 g of 89% phosphoric acid (manufactured by Lhasa Kogyo Co., Ltd.) was added dropwise over 4 hours. After completion of the addition, the mixture was aged at the same temperature for 2 hours. Thereafter, the mixture was heated to 95 ° C. and aged for 4 hours while introducing nitrogen from the bottom at 5 m ³ / hr, and it was confirmed that 90% or more of the reaction water was distilled into the test tube. Was completed, and 1091 g (B1 compound) of a phosphoric ester compound was obtained. The ratio of phosphoric acid monoester / phosphoric diester / phosphoric triester calculated by measuring the acid value of the B1 compound was 40/60/0 (mass%).

Production Example 5
As shown in Table 1, except that the number of added moles of alkylene oxide and the kind of alcohol in the alcohol AO adduct were changed, the phosphate ester compound B2 of the present invention and B3 was produced.

Production Example 6
A stainless steel autoclave equipped with nitrogen and ethylene oxide introduction tubes was charged with 140 g of methanol, and then with 0.10 g of sodium methoxide. Thereafter, the system was purged with nitrogen, 385 g of ethylene oxide was introduced at a reaction temperature of 120 ° C., and then aging was performed at 125 ° C. for 45 minutes to obtain 525 g of a polyethylene glycol monomethyl ether synthesis solution. By distilling the synthesis solution, a fraction having an addition mole number of ethylene oxide of 1 mol was removed to obtain a C1 compound. When the composition of this compound was measured by gas chromatography, the content of polyethylene glycol monomethyl ether having 2 moles of ethylene oxide added was 99.5%. The average molecular weight was 120.

Production Example 7
As shown in Table 2, polyethylene glycol monomethyl ethers C2 and C3 were produced in the same procedure as in the production example of the C1 compound except that the number of added moles of alkylene oxide in the alcohol AO adduct was changed.

<Adjustment of admixture for concrete>
The polycarboxylic acid-based high-performance AE water reducing agent is adjusted as a 20% aqueous solution. The polyalkylene glycol compound obtained in Production Examples 1 to 7, the phosphate ester compound, and polyethylene glycol monomethyl ether were mixed in the proportions shown in Tables 4 to 6, and the antifoaming agent composition was adjusted. A 0.2% antifoaming agent was mixed with the 20% aqueous solution of the polycarboxylic acid polymer to adjust the admixture for concrete, and then filled into a transparent glass container.

<Compatibility test of antifoam in admixture>
The concrete admixture mixed with the antifoaming agent was visually checked for compatibility with the admixture while being appropriately mixed and stirred at 20 ° C. for 28 days. The results are shown in Tables 4-6.
(Compatibility evaluation criteria)
The concrete admixture after 28 days at 20 ° C. was visually observed, and the compatibility was evaluated according to the following evaluation criteria.
A: The antifoaming agent is dissolved in the admixture, and the solution is transparent. Adhesion and separation are not confirmed.
○: The antifoaming agent is dissolved in the admixture, and adhesion and separation are not confirmed, but it is cloudy.
Δ: The antifoaming agent becomes cloudy in the admixture, and white stripes are seen on the upper surface of the container. The adhesion to the container wall is intense.
X: The antifoaming agent is completely separated in the admixture. The adhesion to the container wall is intense.

<Fresh property test>
After adding an antifoaming agent to the admixture and conducting the above compatibility test after lapse of 28 days at 20 ° C., 1.0% of each admixture was added to ordinary Portland cement, and the concrete composition shown in Table 3 below A fresh concrete test was conducted. The concrete was mixed using a 55-liter forced biaxial mixer, and each of the admixtures was added in advance to the coarse aggregate, cement, and fine aggregate, and the mixture was mixed for a predetermined time. The results are shown in Tables 4-6.
Thereafter, immediately after the concrete was discharged, a slump test (JIS A 1101) and an air amount measurement (JIS A 1128) were performed as a fresh concrete test.

<Compressive strength test>
The concrete immediately after the preparation in the section of the fresh concrete test was filled into a φ10 × 20 cm mold. Compressive strength was measured for 28 days in accordance with JIS A 1108 for specimens that were demolded and sealed for 28 days after sealing for one day. Moreover, about the concrete test body (age age 28 days) obtained by the said procedure, the external appearance (the number of coarse bubble marks) was evaluated on the following references | standards. The results are shown in Tables 4-6.
(Evaluation criteria for appearance (large number of coarse bubble marks))
A: No coarse bubble mark is observed on the surface of the test piece. O: A small coarse bubble mark is observed on the surface of the test piece.
X: Coarse bubble marks are conspicuously observed on the surface of the specimen.

As shown in Tables 4 to 5, Examples 1 to 14 using the antifoam composition of the present invention are excellent in compatibility in the admixture without reducing the defoaming property and strength development. It was found that the concrete surface has few coarse bubble marks and can produce a concrete having a good surface appearance.
On the other hand, as shown in Table 6, Comparative Examples 1 to 4 had the same defoaming property and strength development as those using the antifoam composition of the present invention. The solubility was inferior and the surface appearance of the produced concrete was also inferior.

Claims

The following general formula (1):
R 1 O— (A 1 O) n1 —R 2 (1)
(Where
R 1 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an acyl group having 2 to 30 carbon atoms,
R 2 represents a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A 1 O represents an oxyalkylene group having 2 to 4 carbon atoms,
n1 represents an integer of 6 to 100. )
Or the following general formula (2):
R 4 O— (A 2 O) n2 —R 3 O— (A 3 O) n3 —R 5 (2)
(Where
R 3 represents a divalent hydrocarbon group having 1 to 30 carbon atoms,
R 4 and R 5 each independently represent a hydrogen atom or an acyl group having 2 to 30 carbon atoms,
A 2 O and A 3 O each independently represents an oxyalkylene group having 2 to 4 carbon atoms,
n2 and n3 represent 0 or a positive integer whose sum is an integer of 6 to 100. )
A polyoxyalkylene compound (A) represented by:
The following general formula (3):

(Where
R 6 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
A 4 O represents an oxyalkylene group having 2 to 4 carbon atoms,
p represents 0 or an integer of 1 to 50;
q represents an integer of 1 to 3,
M represents a hydrogen atom, an alkali metal atom, a Group 2 metal atom, an ammonium group, or an organic ammonium group. )
The antifoamer composition containing the phosphate compound (B) shown by these.
The defoamer composition according to claim 1, wherein the mass ratio (A) / (B) of the polyoxyalkylene compound (A) and the phosphate ester compound (B) is 99/1 to 60/40.
Furthermore, the following general formula (4):
R 7 O— (A 5 O) m —H (4)
(Where
R 7 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms,
A 5 O represents an oxyalkylene group having 2 to 3 carbon atoms,
m represents an integer of 1 to 5. )
The antifoamer composition of Claim 1 or 2 containing the glycol ether (C) which has a structure represented by these.
The polyoxyalkylene compound (A) represented by the general formula (1) is represented by the following general formula (5):
R 1 ' O- (EO) k -R 2 ' (5)
(Where
R 1 ′ represents an unsaturated fatty acid residue having 12 to 30 carbon atoms,
R 2 ′ represents a hydrogen atom or an unsaturated fatty acid residue having 12 to 30 carbon atoms,
EO represents an oxyethylene group,
n4 represents an integer of 6 to 100. )
The antifoamer composition of any one of Claims 1 thru | or 3 containing the polyoxyalkylene compound (A ') shown by these.
The admixture for hydraulic compositions containing the antifoamer composition of any one of Claims 1 thru | or 4.