JP6398738B2 - Air-entraining agent for cement-based material, cement-based material containing the air-entraining agent, and method for producing the same - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an air entraining agent for cement-based materials, a cement-based material including the air-entraining agent, and a method for producing the same. The present invention relates to an agent, a cement-based material containing the air entraining agent, and a method for producing the same.

  In general, in order to ensure the frost damage resistance of cured mortar or concrete and to improve the resistance to freezing and thawing, it is necessary to entrain fine air bubbles in cementitious materials such as mortar or concrete, and therefore air An entraining agent is contained in the cementitious material.

  Conventionally, as an air entraining agent, a surfactant called an AE agent utilizing a foaming action among surfactants is often used. In general, when water contained in a cement composition freezes, the volume increases and an expansion pressure may be generated. However, if entrained air bubbles formed by such an air entraining agent are present, bubbles are not frozen. This pressure can be relieved through water, and destruction such as cracks due to the expansion pressure of concrete can be prevented.

As such an air entraining agent, an AE agent mainly composed of a surfactant such as a resin acid salt, a higher alcohol sulfate ester salt or an alkylbenzene sulfate ester is generally used. For example, JP 2002-68797 A (Patent Document 1) contains (A) a compound obtained by adding an alkylene oxide to a polyhydric alcohol ester of a hydroxy fatty acid and (B) a fatty acid salt having 8 to 24 carbon atoms, and (A) and (B) The air entraining agent characterized in that the ratio (weight) of (A) / (B) = 1/99 to 99/1 is described.
JP 2013-133261 A (Patent Document 2) discloses polypropylene glycol (A component) having an average molecular weight of 200 to 500, rosin acid (B component), and an HLB value represented by the general formula (I) of 8 or less. Compound (C component) and water, A component and B component in weight ratio, A component: B component = 99.995-99.500: 0.005-0.500, C component as A component And 0.005 to 0.500% by weight of the total weight of the B component, water is contained in a proportion of 5 to 50% by weight in the total weight of the A component, B component, C component and water, and is a transparent liquid at 25 ° C. An air entraining agent is disclosed.

  On the other hand, when grinding cement raw materials and cement clinker, for example, by adding grinding aids such as glycols such as diethylene glycol and alkanolamines such as triethanolamine, the grinding efficiency is improved and the power consumption of the grinding equipment is reduced. Reductions are being implemented.

  As such a grinding aid, JP 2010-116294 A (Patent Document 3) discloses a grinding aid comprising dipropylene glycol monomethyl ether, and further, JP 2011-173836 A (Patent Document). 4) includes propylene glycol, 2,3-butane, having a step of introducing methanol and glycerin as raw materials and introducing hydrogen at a pressure of 0.1 to 20 MPa and reacting at 200 to 280 ° C. in the presence of a copper-containing catalyst. A grinding aid containing a total amount of diol and 1,2-butanediol of 75% by weight or more is described.

  International Publication WO2008 / 038732 (Patent Document 5) discloses glycol-based brake fluid recovered from a vehicle, such as glycol, glycol ether, polyglycol, polyglycol ether, and the like, and a mixture obtained by mixing diethylene glycol with such brake fluid. Is used for grinding aids.

  However, these conventional air entraining agents, which are the above-mentioned AE agents, have no grinding aid effect, while conventional grinding aids have no air entraining action. Moreover, it is only described that the glycols described in Patent Document 5 are used as a grinding aid, and no technical idea about air entrainment is disclosed.

JP 2002-68797 A JP 2013-133261 A JP 2010-116294 A JP 2011-173836 A WO2008 / 038732 Publication

An object of the present invention is to provide a novel air-entraining agent for cement-based materials that solves the above-described problems and can impart good air-entraining properties to the cement-based material. Furthermore, the present invention provides an air-entraining agent for cement-based materials that can impart good air-entraining properties to cement-based materials and can also improve the grinding efficiency of cement clinker and the like. .
Another object of the present invention is to use the air entraining agent of the present invention without using a so-called AE agent, and to achieve good air entrainment without using two types of admixtures of AE agent and grinding aid. It is to provide a cementitious material obtained by improving the pulverization efficiency and its manufacturing method as well as having properties and excellent strength.
The cement-based material is a concept including a cement composition, cement paste, cement mortar, and concrete.

The present inventor has found that among glycols, a specific glycol can impart good air entrainment to a cement-based material and can also function as a grinding aid to improve the grinding efficiency of the cement clinker. The present invention has been completed.
That is, the invention of cement-based material for air-entraining agent, characterized in that it is a triethylene glycol monomethyl ether and / or triethylene glycol butyl ether, cementitious material for air-entraining agent.

Invention of cement-based material comprises a cement and the cement-based material for air-entraining agent, relative to 100 parts by weight of cement, triethylene glycol monomethyl ether and / or triethylene glycol butyl ether 0.01-0.05 It is a cementitious material characterized by containing a mass part.

In the method for producing a cement-based material according to claim 1 , 0.01 to 0.05 parts by mass of triethylene glycol monomethyl ether and / or triethylene glycol butyl ether is added to 100 parts by mass of cement clinker. A method for producing a cementitious material, characterized in that it is prepared by pulverizing and then adding and kneading aggregate and water to the pulverized product.

In another method for producing a cementitious material, a cement clinker is pulverized to produce a cement pulverized product, and then aggregate and triethylene glycol monomethyl ether and / or triethylene glycol butyl ether are added to the pulverized product. For cementitious materials, characterized in that it is prepared by adding and kneading water previously added and blended in an amount of 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the product. It is a manufacturing method.

The air-entraining agent for a cement-based material according to the present invention can impart good air-entraining properties to the cement-based material and can improve the grinding efficiency of a cement clinker or the like.
In addition, since the cementitious material of the present invention contains the air entraining agent of the present invention, it is not necessary to use a so-called AE agent, it has good air entrainment properties, is excellent in strength, and improves the grinding efficiency. Thus, the power consumption of the cement manufacturing equipment such as the grinding equipment can be reduced.
Therefore, the cementitious material of the present invention can improve the freezing and thawing resistance of concrete structures such as roads and buildings, and can effectively prevent cracking of the concrete structures even in cold weather. .

Furthermore, the method for producing a cementitious material of the present invention can efficiently provide good air entrainment to the cementitious material and can effectively produce a cementitious material with improved grinding efficiency.
Therefore, for example, it is possible to save energy when grinding the cement clinker, and it is possible to extend the life of the cement manufacturing facility.

The present invention is illustrated by the following preferred examples, but is not limited thereto.
The invention of the air entraining agent for cement-based materials of the present invention comprises triethylene glycol monomethyl ether and / or triethylene glycol butyl ether as a main component.
Here, the main component is not intended when triethylene glycol monomethyl ether and / or triethylene glycol butyl ether is, for example, triethylene glycol monomethyl ether and / or triethylene glycol butyl ether derived from fluid brake fluid oil. This is not to deny the possibility of including some other ingredients.
Preferably, the air entraining agent for cementitious material of the present invention is made of triethylene glycol monomethyl ether and / or triethylene glycol butyl ether.

  Since triethylene glycol monomethyl ether and / or triethylene glycol butyl ether is also a component of vehicle brake fluid, triethylene glycol monomethyl ether and / or triethylene glycol butyl ether derived from fluid brake fluid oil can be used. In this case, the used waste material taken out at the time of vehicle inspection or dismantling of an automobile or the like can be used, and the resource can be effectively used.

  Such an air entraining agent for cement-based materials according to the present invention imparts air-entraining properties to cement-based materials such as concrete and mortar, and contains an excellent amount of air of about 5% by volume in the cement-based materials. Can do. Thereby, it becomes possible to improve the resistance to freezing and thawing without reducing the strength of the obtained concrete.

In addition, the air-entraining agent for cement-based materials of the present invention is added when the cement clinker is pulverized to a predetermined particle size, so that in addition to the above-mentioned air-entraining action, the action is almost the same as the conventional pulverization aid. And the grinding efficiency of the cement clinker can be increased.
Furthermore, the air-entraining agent for cement-based material of the present invention is not limited to cement clinker pulverization, but also, for example, when cement raw material is pulverized, cement product mixed with cement clinker and gypsum, etc. Can be added to and mixed with an optional pulverization step in the process of manufacturing.

  Therefore, conventionally, when producing a cement-based material having air-entraining properties, it has been necessary to contain an air-entraining agent in addition to the grinding aid, but the novel air-entraining agent of the present invention is Since it exhibits an effect, it saves labor of the manufacturing process and is economically advantageous.

The above-mentioned air-entraining agent for cement-based material of the present invention can be mixed with cement to produce a cement-based material having air-entraining property, for example, so-called AE concrete.
Specifically, the cement-based material of the present invention can be prepared by uniformly kneading cement, the air entraining agent of the present invention, aggregate, water, and additives blended as necessary.
For the kneading, a mixer used for ordinary concrete kneading, for example, an omni-type mixer, a pan-type mixer, a biaxial mixer, or the like can be used. The kneading method is not particularly limited, but generally, the materials may be put into a mixer all at once and kneaded. Moreover, it is good also as a kneaded material by the method of kneading mortar first and sprinkling this on a coarse aggregate.

  In addition, each material may be mixed and used at the time of construction, or a part or all of the material may be mixed in advance. Preferably, cement and other powders are mixed in advance. After the body is prepared, it is desirable to knead the mixed powder with water, aggregate or the like because it can be uniformly and easily kneaded.

  Specifically, for example, 0.01 to 0.05 parts by mass, preferably 0.015 to 0.04 parts by mass of triethylene glycol monomethyl ether and / or triethylene glycol butyl ether with respect to 100 parts by mass of cement clinker. The cement clinker is pulverized by adding a part, and then the aggregate and water are added to the pulverized product and kneaded to increase the pulverization efficiency of the cement clinker, and the resulting cement-based material has excellent air entrainment It is possible to produce a cementitious material that imparts high strength and maintains high strength.

As another method for producing a cementitious material, a cement clinker is pulverized to produce a cement pulverized product, and then the pulverized product is aggregated, and triethylene glycol monomethyl ether and / or triethylene. Add water previously added and blended in an amount such that glycol butyl ether is 0.01 to 0.05 parts by weight, preferably 0.015 to 0.04 parts by weight, with respect to 100 parts by weight of the cement ground product. And kneading.
As described above, by previously mixing the air entraining agent of the present invention with kneaded water, it becomes possible to uniformly mix the air entraining agent in the obtained cementitious material.
Such a method also makes it possible to produce a cement-based material that imparts excellent air entrainment to the resulting cement-based material and maintains high strength.

As the cement used in the present invention, any known cement can be applied, and the type of the cement is not particularly limited, and examples thereof include various portland cements such as normal, early strength, ultra-early strength, moderate heat, and low heat. , Blast furnace cement, silica cement and fly ash cement, various cements available in the market such as white Portland cement and alumina cement, super fast cement, etc., these can be used alone or in combination Can be used.
In addition, the cement used in the present invention includes a blast furnace slag powder, fly ash, silica fume, limestone powder, quartz powder, dihydrate gypsum, which is a material having pozzolanic activity, in order to improve long-term strength and ease drying shrinkage. Adequate amounts of admixtures such as hemihydrate gypsum, type I, type II and type III anhydrous gypsum can be used alone or in combination.
The proportion of cement in the powder is preferably about 60% by mass or more.

Further, the mortar and concrete, which are the cement-based materials of the present invention, contain fine aggregates and coarse aggregates, but the types of these coarse aggregates and fine aggregates are particularly limited. is not.
The fine aggregate contained as needed is not particularly limited, and fine aggregate with a relatively small particle size such as mountain sand, river sand, land sand, crushed sand, sea sand, quartz sand No. 3-7, or silica stone Known fine aggregates such as fine powder such as powder and limestone powder, and mixtures thereof can be used. In the present invention, as the fine aggregate, one that passes 85% by weight or more of a 5 mm sieve specified by the Japan Society of Civil Engineers can be used.

The coarse aggregate is not particularly limited, and any commonly used coarse aggregate can be used. For example, river gravel, land gravel, crushed stone, and the like can be used. As the coarse aggregate, normally, for example, No. 4 to No. 7 crushed stone having a maximum particle size of 5 mm to 30 mm can be used.
The blending ratio is not particularly limited, and can be determined according to the intended use.

Moreover, various additives can be mix | blended with the cement-type material of this invention as needed.
As various additives, any known additive that is added when preparing concrete can be added depending on the application. For example, a setting retarder, a curing accelerator, an antifoaming agent, and a rust inhibitor. In addition, various admixtures such as anti-freezing agents, coloring agents, water reducing agents, high-performance water reducing agents, and reinforcing materials such as carbon fibers and steel fibers for improving durability do not substantially impair the purpose of the present invention. Although it can be used in a range, conventional air entraining agents such as AE agents are not used.

  The cementitious material manufactured in this way can contain an air amount of 5% by volume without causing a decrease in strength, and can exhibit an excellent air entraining action.

The present invention will be described in detail by way of specific examples, comparative examples and test examples, but is not limited thereto.
(Materials used)
The following examples and comparative examples were carried out using the following materials.
・ Normal Portland cement clinker: (Sumitomo Osaka Cement Co., Ltd.)
・ Dihydrate gypsum (natural)
-Coarse aggregate (G): Crushed stone (Nishijima, Hyogo: density 2.56, coarse grain rate 2.72)
・ Fine aggregate (S): River sand (from Yasugawa, Shiga Prefecture: density 2.63, coarse grain ratio 6.62)
・ Water (W): Waterworks (Osaka City Waterworks Bureau)
Admixture (AD): Pozzolith No. 70 (manufactured by BASF Japan Ltd .: AE water reducing agent)
・ Triethylene glycol monoethyl ether: derived from brake fluid oil ・ Triethylene glycol butyl ether: derived from brake fluid oil ・ Diethylene glycol (powder aid): Reagent (Kanto Chemical)
・ Triethanolamine (powder aid): Reagent (Kanto Chemical)
・ Mighty AE-02 (manufactured by Kao Corporation: AE agent, anionic surfactant)
・ Master Air (BASF Japan KK: AE agent, alkyl ether anionic surfactant)
・ Sodium linear dodecylbenzenesulfonate: Reagent, manufactured by Wako Pure Chemical Industries, Ltd .: Anionic surfactant)

(1) Air entrainment (Examples 1-2, Comparative Examples 1-5)
Ordinary Portland cement clinker obtained by pulverizing ordinary Portland cement clinker with a jaw crusher and a brown mill and natural dihydrate gypsum were mixed so that the content of SO ₃ was 2.0% by mass.
To this mixture, triethylene glycol monoethyl ether (Example 1), triethylene glycol butyl ether (Example 2), diethylene glycol (Comparative Example 1), triethanolamine (Comparative Example 2), anionic surfactant mighty Each compound of AE-02 (Comparative Example 3) and master air (Comparative Example 4) of an alkyl ether anionic surfactant was added to 0.03 parts by mass with respect to 100 parts by mass of the mixture.
In addition, Comparative Example 5 was pulverized in the same manner as Example 1 except that nothing was added to the mixture.
The obtained mixture was pulverized with a ball mill to prepare each ordinary Portland cement having a fineness of 3300 cm ² / g (prototype ordinary Portland cement).
Using each prepared normal Portland cement (C), the fine aggregate, coarse aggregate, admixture and water were blended at the blending ratio shown in Table 1 below, and Examples 1-2 and Comparative Examples 1- 5 concretes were prepared.

(Examples 3 to 4)
Ordinary Portland cement clinker obtained by pulverizing ordinary Portland cement clinker with a jaw crusher and a brown mill and natural dihydrate gypsum were mixed so that the content of SO ₃ was 2.0% by mass. The obtained mixture was pulverized with a ball mill to prepare ordinary Portland cement having a fineness of 3300 cm ² / g.
Water (Example 3) or triethylene glycol in which fine aggregate, coarse aggregate, admixture and triethylene glycol monomethyl ether were added in advance to the prepared ordinary Portland cement (C) in the blending ratio shown in Table 1 below. Each concrete of Examples 3 to 4 was prepared by blending water (Example 4) to which butyl ether had been added in advance.
However, triethylene glycol butyl ether or triethylene glycol butyl ether added in advance to water was added to water in advance so that the amount was 0.03 parts by mass with respect to 100 parts by mass of ordinary Portland cement.

(Comparative Example 6)
Ordinary Portland cement clinker obtained by pulverizing ordinary Portland cement clinker with a jaw crusher and a brown mill and natural dihydrate gypsum were mixed so that the content of SO ₃ was 2.0% by mass. The obtained mixture was pulverized with a ball mill to prepare ordinary Portland cement having a fineness of 3300 cm ² / g.
In the prepared ordinary Portland cement (C), fine aggregate, coarse aggregate, admixture, linear sodium dodecylbenzenesulfonate and water were blended at the blending ratio shown in Table 1 below, and the concrete of Comparative Example 6 was blended. Prepared.

(Test Example 1) Strength test For each concrete of Examples 1 to 4 and Comparative Examples 1 to 6, based on the test method defined in JIS R 5201 "Physical Test Method for Cement", the initial and final times of setting, In addition, the compressive strength at the age of 7 and 28 days was measured.
The results are shown in Table 2 below.

(Test example 2) Air entrainment test About each concrete of Examples 1-4 and Comparative Examples 1-6, based on JISA1129-2 "the mortar and concrete length test method 2nd part contact gauge", air quantity Was measured. The slump value was also measured.
The results are shown in Table 2 below.

  From Table 2, in Example 1 and Example 2 of the present invention, the air entraining effect better than Comparative Example 3 and Comparative Example 4 to which a surfactant which is a commonly used air entraining agent is added should be confirmed. I was able to. On the other hand, in Comparative Example 1 and Comparative Example 2, no air entrainment was observed, and an air entrainment effect equivalent to that of Comparative Example 5 without addition was shown.

(2) Grinding aid effect (Examples 5-6, Comparative Examples 7-11)
Ordinary Portland cement clinker obtained by pulverizing ordinary Portland cement clinker with a jaw crusher and a brown mill and natural dihydrate gypsum were mixed so that the content of SO ₃ was 2.0% by mass.
To this mixture, triethylene glycol monoethyl ether (Example 5), triethylene glycol butyl ether (Example 6), diethylene glycol (Comparative Example 7), triethanolamine (Comparative Example 8), anionic surfactant mighty Each compound of AE-02 (Comparative Example 9) and master air (Comparative Example 10) of an alkyl ether anionic surfactant was added to 0.03 parts by mass with respect to 100 parts by mass of the mixture.
In addition, it grind | pulverized like Example 5 except not adding anything to the comparative example 11 and the said mixture.

(Test Example 3) Crushing efficiency test Each obtained mixture was pulverized with a ball mill, the relationship between the pulverization time and fineness was determined, and the results are shown in Table 3 below.

  From Table 3, Example 5 and Example 6 of this invention were able to confirm the powder auxiliary agent effect equivalent to or better than Comparative Example 7 and Comparative Example 8 to which a commonly used powder auxiliary agent was added. On the other hand, Comparative Example 9 and Comparative Example 10 did not show a remarkable dusting agent effect, and showed the same grinding efficiency as Comparative Example 11 without addition.

  Since the present invention is excellent in freeze-thaw properties, it can be applied to various uses of civil engineering structures and building structures such as road pavements such as sidewalks and roadways in cold districts, revetments of rivers, and the like.

Claims (1)

  Triethylene glycol monomethyl ether and / or triethylene glycol butyl ether is added in an amount of 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the cement clinker, and then the cement clinker is pulverized. A method for producing a cementitious material, characterized by being prepared by adding water and kneading.