JP2003313059A - Foaming agent for foamed mortar - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foaming agent which has excellent foaming power, foam stability and non-water absorbency and non-water permeability of a foamed mortar hardening body. <P>SOLUTION: The foaming agent consists of one or more kinds of foaming components (A) selected from the group consisting of an alkylbenzenesulfonate expressed by formula (1) (wherein, R is an 8 to 50C aliphatic hydrocarbon group; and M is hydrogen, zinc, an alkali metal or an alkaline-earth metal), an alpha-olefinsulfonate expressed by general formula 2: R<SB>1</SB>CH=CH(CH<SB>2</SB>)<SB>n</SB>SO<SB>3</SB>Z (wherein, R<SB>1</SB>is an 8 to 30C aliphatic hydrocarbon group; n is 0 to 5; and Z is an alkali metal or an alkaline-earth metal; and a polyoxyethylene alkyl ether sulfate expressed by formula (3) (wherein, R<SB>2</SB>is an 8 to 20C aliphatic hydrocarbon group; A is hydrogen or a methyl group; m is a number between 0 and 1 (excluding 0 and 1); and X is an alkali metal, ammonium or an amine cation, and an 8 to 20C aliphatic alcohol (B). <P>COPYRIGHT: (C)2004,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foaming agent for cellular mortar. [0002] Conventionally, it has been known that polyoxyethylene alkyl ether sulfate is used as a foaming agent for foam mortar, and a water-soluble polymer such as various cellulose derivatives or polyvinyl alcohol is used in combination as a foaming stabilizer. Have been.
Further, as disclosed in Japanese Patent Publication No. 6-45511, a method is known in which a polyoxyethylene alkyl ether sulfate is used in combination with an aliphatic alcohol. [0003] However, although these foaming agents are excellent in the foaming power, they cannot be said to be sufficient in terms of the stability of the foams.
The impermeability was not sufficient. [0004] Therefore, an object of the present invention is to provide a foaming agent which is used in a foam mortar and has excellent foaming power and bubble stability, and also has excellent non-water absorption and non-water permeability of a cured mortar. It was done as. That is, the foaming agent for cellular mortar of the present invention has a general formula: (Wherein R is an aliphatic hydrocarbon group having 8 to 50 carbon atoms, M is hydrogen, zinc, an alkali metal, or an alkaline earth metal), and a general formula R ₁ CH = CH (CH ₂ ) _n SO ₃ Z (2) (wherein, R ₁ is an aliphatic hydrocarbon group having 8 to 30 carbon atoms, n
Is 0 to 5, and Z is an alkali metal or an alkaline earth metal. ) And the general formula (Wherein, R ₂ represents an aliphatic hydrocarbon group having 8 to 20 carbon atoms, A
Is a hydrogen or methyl group, m is a number between 0 and 1 (0 and 1
, X is an alkali metal, ammonium, or amine cation. 1) selected from the group consisting of polyoxyethylene alkyl ether sulfates represented by
A foaming component (A) composed of one or more species and a carbon number of 8
-20 aliphatic alcohols (B). [0006] Foaming component (A) and aliphatic alcohol (B)
Is usually 99.9: 0.1 to 1 in terms of a pure weight ratio.
0:90 is preferable, and preferably 9:90.
9: 1 to 50:50. If the foaming component (A) is less than 10, the foaming power tends to decrease, and if the aliphatic alcohol (B) is less than 0.1, the bubble stability tends to be poor. [0007] The foaming component (A) in the present invention
Is an alkylbenzene sulfonate represented by the general formula (1), an alpha-olefin sulfonate represented by the general formula (2) or a polyoxyethylene alkyl ether sulfate represented by the general formula (3) alone or And two or more types selected from the following may be used in combination. The aliphatic hydrocarbon group having 8 to 50 carbon atoms represented by R in the general formula (1) is a saturated or unsaturated linear or branched alkyl group. For example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
Examples include a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, an oleyl group, a linoleyl group, and a linolenyl group. Among these, an alkyl group having 8 to 20 carbon atoms is preferable from the viewpoint of foaming power, and a particularly preferable one is a dodecyl group. M is hydrogen, zinc, or an alkali metal or alkaline earth metal, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and radium. Of these, hydrogen, zinc, sodium, potassium, magnesium, calcium, and barium are preferred, and sodium, potassium, magnesium, and calcium are particularly preferred. In the method for producing an alkylbenzene sulfonate represented by the general formula (1), when the alkyl group has a branched type, for example, propylene is polymerized using a phosphoric acid catalyst to obtain propylene tetramer (tetramer). after, the tetramer hydrogen fluoride, sulfuric acid, aluminum chloride by benzene and the reaction (alkylation) as a catalyst and dodecylbenzene, a method can be adopted sulfonating blowing contact method SO ₃ gas thereto. On the other hand, when the alkyl group has a linear type, for example, a linear paraffin chlorinated product is thermally decomposed into an n-olefin and hydrogen chloride gas, and benzene is alkylated with the n-olefin to form a linear alkylbenzene, which is then contacted. A method of sulfonating by blowing SO ₃ gas can be adopted. The aliphatic hydrocarbon group having 8 to 30 carbon atoms represented by R ₁ in the general formula (2) is a saturated or unsaturated linear or branched hydrocarbon group. For example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
Examples include a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, an oleyl group, a linoleyl group, and a linolenyl group. Among them, a hydrocarbon group having 8 to 20 carbon atoms is preferable from the viewpoint of foaming power, and a tetradecyl group is particularly preferable. N represents the average number of moles of the methyl group,
Range. If the number of added moles exceeds 5, the non-water-absorbing and non-water-permeable properties of the cellular mortar deteriorate. Z is an alkali metal or an alkaline earth metal, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium and a mixture of two or more of these. Of these,
Sodium, potassium, magnesium, calcium and barium are preferred, and sodium, potassium and calcium are particularly preferred. The alpha olefin sulfonate represented by the general formula (2) can be produced by sulfonation of an alpha olefin, but is usually obtained as a mixture of an alkenyl sulfonate and a hydroxyalkane sulfonate. Available as a mixture. The aliphatic hydrocarbon group having 8 to 20 carbon atoms represented by R ₂ in the general formula (3) is a saturated or unsaturated linear or branched alkyl group. For example, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
Examples include a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, an oleyl group, a linoleyl group, and a linolenyl group. Among these, an alkyl group having 10 to 16 carbon atoms is preferable, and a particularly preferable example is a dodecyl group. If the number of carbon atoms is less than 8 or more than 20, the foaming power is lowered and a cured product having a desired specific gravity cannot be obtained. M represents the average number of moles of ethylene oxide or propylene oxide, and is a number between 0 and 1 (not including 0 and 1). When the average number of moles is 1 or more, the non-water-absorbing property and the non-water-permeable property of the cellular mortar deteriorate. X represents a counter ion of an alkyl sulfate, and examples thereof include alkali metals (such as lithium, sodium and potassium), ammonium, amine cations (such as alkylamine and alkanolamine), and mixtures of two or more thereof. The aliphatic alcohol (B) is for stabilizing the foam, and is a linear or branched, natural or synthetic, saturated or unsaturated primary or secondary monohydric alcohol having 8 to 20 carbon atoms, for example, Examples include octyl alcohol, decyl alcohol, lauryl alcohol (dodecyl alcohol), myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosyl alcohol, synthetic alcohols, and mixtures of two or more of these. Of these, lauryl alcohol, myristyl alcohol and cetyl alcohol are preferred. The foaming agent of the present invention may contain, if necessary, a fatty acid, a water-soluble inorganic metal salt, a nonionic surfactant, an amphoteric surfactant, a water-soluble organic solvent, a water-soluble polymer, a cationic surfactant, a water reducing agent. An agent and a dispersant may be used in combination. In particular, fatty acids are effective in improving the non-absorbent and non-permeable properties of the foam mortar, and the nonionic surfactant smoothes the bubbles,
It has the effect of suppressing the generation of coarse foam in the cement slurry. Fatty acids include linear or branched natural or synthetic saturated or unsaturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, tallow fatty acid,
Oleic acid, castor hardened fatty acid, linoleic acid, palmitoleic acid, linolenic acid and the like, and one or a mixture of two or more of these. Among these, preferred are stearic acid and palmitic acid. The amount of the fatty acid to be added is generally 0.01 to 50 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the foaming component (A) and the aliphatic alcohol (B). Examples of the water-soluble inorganic metal salts include sodium salts (eg, sodium sulfate and sodium chloride), potassium salts (eg, potassium sulfate, potassium chloride), magnesium salts (eg, magnesium sulfate, magnesium chloride), and calcium salts (eg, sulfuric acid). Calcium, calcium chloride, etc.) and one or a mixture of two or more thereof. Of these, preferred are magnesium sulfate and sodium sulfate. The amount of the water-soluble inorganic metal salt to be added is generally 0 to 50 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight in total of the foaming component (A) and the aliphatic alcohol (B). Examples of the nonionic surfactant include alkyl ether type, alkyl phenol type, alkyl ester type, sorbitan ester type and sorbitan ester ether type. One or a mixture of two or more of these may be mentioned. Of these, alkyl ether type is preferred. The addition amount of the nonionic surfactant is 1 in total of the foaming component (A) and the aliphatic alcohol (B).
The amount is usually 0 to 100 parts by weight, preferably 1 to 30 parts by weight based on 00 parts by weight. A water-soluble organic solvent which does not inhibit foaming properties. For example, cellosolve solvents (methyl cellosolve,
Ethyl cellosolve, butyl cellosolve, etc.), carbitols (ethyl carbitol, butyl carbitol, etc.), polyoxyethylene lower alkyl ethers having 3 to 10 moles of added ethylene oxide, diols (ethylene glycol, diethylene glycol, etc.) and these A mixture of two or more types is exemplified. Of these, cellosolve solvents and diols are preferred, and butyl cellosolve, isobutyl cellosolve, ethylene glycol and diethylene glycol are preferred. The amount of the water-soluble organic solvent to be added is usually 0 to 100 relative to the total of 100 parts by weight of the foaming component (A) and the aliphatic alcohol (B).
Parts by weight, preferably 5 to 70 parts by weight. Examples of the water-soluble polymer include cellulose derivatives (eg, methylcellulose, hydroxyethylcellulose), polyvinyl alcohol, sodium alginate, polyvinyl ether, and mixtures of two or more of these. Preferably, the cellulose derivatives are used. . The amount of the water-soluble polymer to be added is usually 0 to 3 based on 100 parts by weight of the total of the foaming component (A) and the aliphatic alcohol (B).
0 parts by weight, preferably 0.01 to 20 parts by weight. Examples of the cationic surfactant include those which do not impair the foaming property, such as monoalkylammonium chloride, dialkylammonium chloride, EO-added ammonium chloride, tetramethylammonium chloride, and benzyltrimethylammonium chloride. Preferred is a monoalkylammonium chloride. The amount of cationic surfactant added
A total of 100 of the foaming component (A) and the aliphatic alcohol (B)
Usually 0 to 100 parts by weight, preferably 1 to 100 parts by weight
30 parts by weight. The amphoteric surfactants do not impair the foaming properties and include, for example, alanine type, imidazolinium betaine type, aminopropyl betaine type, aminodipropion type and the like. Preferably, it is of the imidazolinium betaine type. The amount of the amphoteric surfactant to be added is generally 0 to 100 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the foaming component (A) and the aliphatic alcohol (B). The water reducing agent does not impair the foaming property and includes, for example, polycarboxylic acid type, lignin type, sulfamine type, naphthalene sulfonic acid type and alkyl sulfate ester salts. Preferably it is a polycarboxylic acid type. The amount of the water reducing agent to be added is usually 0 to 10 with respect to 100 parts by weight of the total of the foaming component (A) and the aliphatic alcohol (B).
0 parts by weight, preferably 1 to 50 parts by weight. The dispersing agent does not impair the foaming property and includes, for example, naphthalenesulfonic acid type, alkylnaphthalenesulfonic acid type, polycarboxylic acid type, polystyrenesulfonic acid type, alkylamine type, alkylphenol type and the like. Preferably it is a polycarboxylic acid type. The amount of the dispersant added is usually 0 to 100 based on 100 parts by weight of the total of the foaming component (A) and the aliphatic alcohol (B).
Parts by weight, preferably 1 to 50 parts by weight. The foaming agent of the present invention is generally used for cement,
It is used as a cellular mortar composition together with water or cement, water, aggregate and the like. Even if the mortar composition is used as it is without forming bubbles, non-water-permeable and non-water-absorbing effects can be obtained. Examples of the cement include ordinary Portland cement, early-strength Portland cement, fly ash cement, blast furnace cement and the like, and are not affected by the type of cement at all. Examples of the water include tap water, groundwater, seawater, and the like. The type of the aggregate is not particularly limited, and examples thereof include ordinary sand, crushed stone, quartz sand, lightweight aggregate (such as perlite and shirasu balloon). In the present invention, as long as the foaming effect of the foaming agent is not impaired, various conventionally used cement admixtures can be used together if necessary. These cement admixtures include known cement dispersants (lignin, melamine, naphthalene, etc.), setting retarders (polyphosphate, citrate, etc.), curing accelerators (calcium chloride, etc.), shrinkage reduction Agents (lower alcohols and the like), water repellents (higher fatty acids and the like), quick-setting agents (calcium aluminate and the like), blast furnace slag, silica fume, gypsum and volcanic ash. The foaming agent of the present invention requires a lightweight foam mortar, such as concrete or mortar, which is used for civil engineering and construction purposes, and concrete or mortar secondary products produced in factories. Various cementitious cured products can be mentioned. When the foaming agent of the present invention is used for the production of lightweight mortar, a method of prefoaming the foaming agent in the form of an aqueous solution and adding the foam to a cement slurry (preform method) In addition, there is a method in which a foaming agent is foamed together with other materials while stirring in a mixer (mix foam method), but any method may be used. When the lightweight foam mortar is produced by the preform method, the foaming component and the aliphatic alcohol component of the present invention are formulated as a compound, and if necessary, in the form of an aqueous solution using a water-soluble organic solvent or the like. After foaming using a foaming device or a mixer, the foam is mortar-produced by kneading cement, water, aggregate, etc., and then adding and mixing the so-called cement slurry. When the lightweight foam mortar is produced by the mix foam method, the method of adding the foaming agent of the present invention is not particularly limited. Usually, cement and aggregate are mixed, and when the kneading water is added, the foaming component and the aliphatic compound are mixed. It is desirable to add an alcohol component or other components as a blend, if necessary, in the form of an aqueous solution using a water-soluble organic solvent, but after kneading the cement, water and aggregate, a so-called cement slurry is formed. Alternatively, it may be added to the cement or the aggregate in advance, and then water may be added. Further, even if the foaming agent components are separately added to the present invention individually or simultaneously or sequentially at the stage of the kind of the kneading step, there is no adverse effect on the performance. The method of applying the mortar and concrete containing the product of the present invention may be the same as that of the conventional case, and various methods such as filling into a mold and pouring with a caulking gun can be employed. The curing method may be any one of air-dry curing, wet-air curing, and heat-curing curing (steam curing, autoclave curing, etc.), and each curing method may be used in combination. EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. [Examples 1 to 5] [Comparative Examples 1 and 2] Foaming component (A) and aliphatic alcohol (B) shown in Table 1
Was used to make (A) :( B) = 95: 5 (pure weight ratio), and the foaming agents of the present invention were prepared in combinations shown in Table 2. As a comparative example, sodium polyoxyethylene alkyl ether sulfate (trade name “Alscope D
A-330 "manufactured by Toho Chemical Industry Co., Ltd .; alkyl group having 12 or 13 carbon atoms; mole number of polyoxyethylene 3) and aliphatic alcohol, sodium polyoxyethylene alkyl ether sulfate (trade name" Alscope DA-330 ") ")
And water-soluble polymer carboxymethylcellulose (C
MC) (trade name “CMC Daicel 1120” manufactured by Daicel Chemical Industries, Ltd.) was used to prepare a foaming agent. [Table 1] [Table 2] [Examples 6 to 10] [Comparative Examples 3 and 4] Using the foaming agents prepared in Examples 1 to 5 and Comparative Examples 1 and 2, preforms were made using the materials shown in Table 3. A lightweight foam mortar was prepared by the method. These compositions were subjected to a foaming test, a water absorption test, and a water permeability test. That is, Examples 1 to 5 and Comparative Examples 1 and 2
5% by volume of fresh foaming agent (ground water)
Table 4 shows the results obtained by measuring the maximum foaming ratio of bubbles produced by diluting with a seawater and diluting the diluted solution with a foaming machine. [Table 3] [Table 4] Similarly, each of the foaming agents of Examples 1 to 5 and Comparative Examples 1 and 2 was mixed with fresh water (ground water) so as to be 5% by volume.
The foam (20-fold foaming: 50 g / 1 L) produced from the diluted solution using a foaming machine is charged with cement, sand, and water in the ratio shown in Table 3 into a mortar mixer and mixed for 1 minute. The lightweight mortar (air mortar) obtained by adding to the mortar obtained by the above and mixing by hand mixing was used to obtain 4 × 4 × 16 cm and φ10 × 20 cm.
, And subjected to wet-air curing (20 ° C., 24 hours) to obtain a foam mortar. Table 5 shows the results of a water absorption test using a 4 × 4 × 16 cm cell mortar and a water permeability test using a φ10 × 20 cm cell mortar. [Water absorption test] The water absorption test was carried out according to "6.4 Water absorption test" in JIS A5423 "Residential asbestos slate for house roof". One test specimen (4 × 4 × 16 cm)
Put in an air dryer with a stirrer adjusted to 05 ± 5 ° C,
After drying for 4 hours, take out, put in a desiccator adjusted with silica gel, cool to room temperature and measure the weight when dried. Next, it is immersed in water at 20 ± 3 ° C. for 24 hours, the moisture in the inundated portion is quickly wiped off, and the weight immediately weighed is taken as the weight at the time of water absorption. The water absorption is determined by the following equation. Water absorption (%) = 100 × {(mass when water is absorbed−mass when dried) / mass when dried} [Water permeability test] “6.6 Water permeability” in JIS A5423 “Cosmetic asbestos slate for house roof” Sex test ". The test piece (φ10 × 20 cm) was allowed to stand so that the top surface was horizontal, and an acrylic pipe with an inner diameter of about 35 mm and a height of about 300 mm was set up at the center of the top face, and the bottom end of the pipe was in contact with the top face of the test piece. Seal the part using oily soil. Next, water is poured to a height of 250 mm from the bottom end of the tube, and the tube is allowed to stand still for 24 hours, and then the water level is measured. The lower the water level, the greater the water permeability. [Table 5] As is clear from the results shown in Table 4, the foaming agent of the present invention was found to have excellent foaming power in both fresh water and seawater dilution. Further, from the results in Table 5, it was found that the use of the foaming agent of the present invention makes the cured cellular mortar excellent in non-water absorption and non-water permeability. Separately, the cured coagulated material was cut in the transverse direction and the state of bubbles inside was observed. As a result, the cured products using the foaming agent of the present invention showed that fine bubbles were uniformly dispersed. On the other hand, the cured products using the foaming agents of Comparative Examples 1 and 2 exhibited shrinkage and coarse foam. The foaming agent of the present invention has a good foaming power in the production of lightweight cellular mortar, and is excellent in the water-impermeable and non-water-absorbing properties of the mortar. Further, even when the foam mortar produced by using the foaming agent of the present invention is poured into a place where stored water or spring water is present, material separation of the foam mortar hardly occurs, and internal bubbles are dissipated. Hard to do. Therefore, by using the foaming agent of the present invention, it is possible to produce a lightweight mortar with stable quality, which is useful for weight reduction for construction and civil engineering.

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[Procedure amendment] [Submission date] May 13, 2002 (2002.5.1)
3) [Procedure amendment 1] [Document name to be amended] Description [Item name to be amended] 0023 [Correction method] Change [Content of amendment] Examples of the water-soluble polymer include cellulose derivatives (methylcellulose, hydroxy Ethylcellulose), polyvinyl alcohol, sodium alginate, polyvinyl ether, and mixtures of two or more thereof, and are preferably cellulose derivatives. The addition amount of the water-soluble polymer is generally 0 to 100 parts by weight of the total of the foaming component (A) and aliphatic <br/> alcohol (B)
It is 30 parts by weight, preferably 0.01 to 20 parts by weight. [Procedure amendment 2] [Document name to be amended] Description [Item name to be amended] 0025 [Amendment method] Change [Content of amendment] As an amphoteric surfactant, it does not inhibit foaming properties. Type, imidazolinium betaine type, aminopropyl betaine type, aminodipropion type and the like. Preferably, it is of the imidazolinium betaine type. Amount of both sex field surface active agent is usually 0-100 parts by weight per 100 parts by weight of the foaming component (A) and an aliphatic alcohol (B), preferably 1 to 30 parts by weight. [Procedure amendment 3] [Document name to be amended] Specification [Item name to be amended] 0040 [Amendment method] Change [Content of amendment] [Table 2] ────────────────────────────────────────────────── ───
[Procedure amendment] [Date of submission] August 2, 2002 (2002.8.2) [Procedure amendment 1] [Document name to be amended] Specification [Item name to be amended] 0012 [Correction method] Change [Amendment] N represents the average number of moles of a methylene group,
5 range. If the number of added moles exceeds 5, the non-water-absorbing and non-water-permeable properties of the cellular mortar deteriorate.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C04B 103: 48 C04B 103: 48 (72) Inventor Yasuyuki Hiratsuka 1-6-4 Minamidai, Kawagoe-shi, Saitama No. Daiichi Kasei Sangyo Co., Ltd. Kawagoe Factory (72) Inventor Chiaki Endo 1-6-4 Minamidai, Kawagoe-shi, Saitama Prefecture Daiichi Kasei Sangyo Co., Ltd. Kawagoe Factory (72) Inventor Takuji Saito Chiyoda-ku, Tokyo Daiichi Kasei Sangyo Co., Ltd. 3-72, Kanda Jimbocho Daiichi Kasei Sangyo Co., Ltd. (72) Inventor Minoru Nakata 3-7-1 Kanda Jimbocho, Chiyoda-ku, Tokyo

Claims (1)

[Claim 1] The general formula is (Wherein R is an aliphatic hydrocarbon group having 8 to 50 carbon atoms, M is hydrogen, zinc, an alkali metal, or an alkaline earth metal), and a general formula R ₁ CH = CH (CH ₂ ) _n SO ₃ Z (2) (wherein, R ₁ is an aliphatic hydrocarbon group having 8 to 30 carbon atoms, n
Is 0 to 5, and Z is an alkali metal or an alkaline earth metal. ) And the general formula (Wherein, R ₂ represents an aliphatic hydrocarbon group having 8 to 20 carbon atoms, A
Is a hydrogen or methyl group, m is a number between 0 and 1 (0 and 1
, X is an alkali metal, ammonium, or amine cation. 1) selected from the group consisting of polyoxyethylene alkyl ether sulfates represented by
A foaming component (A) composed of one or more species and a carbon number of 8
A foaming agent for cellular mortar, characterized in that the foaming agent comprises from 20 to 20 aliphatic alcohols (B).