JPS59128241A - Shrinkage decreasing agent effective for cement - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to cement shrinkage reducing agents.

Conventionally, one of the serious drawbacks of cement mortar and concrete (hereinafter referred to as cement compositions) is that they are susceptible to dry cracking. This is due to the large drying shrinkage of cement. Therefore, it is desired to reduce drying shrinkage of cement compositions.

In order to reduce the drying shrinkage of cement compositions, a method of mixing latex such as acrylic latex or synthetic rubber latex into the cement composition has been used, but in this case, relatively expensive latex is used. Since it is necessary to mix a large amount (for example, about 20 to 30% by weight with respect to cement), this is not only economically undesirable, but also causes a fatal defect in that the strength of the cement composition is significantly reduced. Furthermore, the incorporation of a large amount of latex causes a serious drawback in that the nonflammability of the cement composition is impaired.

Furthermore, although inorganic expandable admixtures (for example, calcium sulfoaluminate-based expandable admixtures) have been developed in recent years, they are not sufficient to essentially reduce drying shrinkage.

Under such circumstances, the inventors conducted intensive studies on cement shrinkage reducing agents that do not have the above-mentioned drawbacks, and as a result, they arrived at the present invention.

That is, the present invention is based on the general formula (1) (% formula % ) ) (wherein,
7 cycloalkylamine or a residue obtained by removing (m+β) active hydrogens from a polyamine having 2 to 10 carbon atoms, A and N are alkylene groups, and Y is a polycarboxylic acid with two carboxyl groups removed. residue, (n x m
+dXβ) is a number from 1 to 10 when X is an aliphatic amine residue or a cycloalkylamine residue;
is a polyamine residue, the number is 4 to 20, m is 1 to 4
, β is a number from 0 to 4, O is a number from 1 to 4, and M is an ion of hydrogen, alkali metal, alkaline earth metal, or ammonium). The present invention is a cement shrinkage reducing agent which has an improved shrinkage reducing effect and contains the aminocarboxylic acid type compound and a fluorosurfactant or/and a silicone surfactant.

1 carbon number as the X residue constituting the general formula (1) of the present invention
Examples of aliphatic amines of ~7 include methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, 2-ethylbutylamine, dimethylamine, diethylamine, dipropylamine, methylethylamine, methylpropylamine. , methylpentylamine, ethylpropylamine, ethylbutylamine, etc., and examples of cycloalkylamines having 4 to 7 carbon atoms that serve as the X residue include:
Examples include cyclobutylamine, cyclopentylamine, cyclohexylamine, methylcyclohexylamine, and the like. Examples of polyamines having a total carbon number of 2 to 10 include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenebentamine, pentaethylenehexamine, piperazine, propylenediamine, and hexamethylenediamine, and aromatic polyamines such as xylylenediamine. alicyclic polyamines such as hexahydroxylylene diamine, isophorone diamine, m
- Aromatic polyamines such as phenylene diamine, etc. can be mentioned. Among these various amines, aliphatic amines are preferable because they can further improve the shrinkage reduction effect, and in particular, aliphatic amines with 3 carbon atoms
Aliphatic amines having ~5 alkyl groups are preferred. Use of an amine having an alkyl group or cycloalkyl group having 8 or more carbon atoms not only reduces the shrinkage reducing effect but also entrains air into the cement composition, resulting in a decrease in strength, which is undesirable.

Examples of the polycarboxylic acid constituting Y in the general formula (1) of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, and sebacic acid. Aliphatic saturated dicarboxylic acids, aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, tricarboxylic acids such as tricarballylic acid and benzenetricarboxylic acid, etc. can be used. Among these polycarboxylic acids, saturated and unsaturated dicarboxylic acids having 1 to 4 carbon atoms other than the carboxyl group are preferred from the viewpoint of shrinkage reducing effect. Examples of these dicarboxylic acids include malonic acid, succinic acid, glutaric acid,
Examples include adipic acid, maleic acid, and fumaric acid, and particularly preferred are succinic acid, maleic acid, and fumaric acid.

In the general formula (1) of the present invention, −+AO+n or +
Alkylene oxides constituting A'o'yrt include ethylene oxide and propylene oxide. Also,
In the present invention, the total number of moles of these alkylene oxides (
nxm+rrxl is a number from 1 to 10 when X is an aliphatic amine residue or a cycloalkyl amine residue. When this number exceeds 10, air is entrained in the cement composition, which not only reduces the strength of the composition but also reduces the shrinkage reduction effect1, which is not preferable. Also,
Even if X is a polyamine residue (nxm+yxβ)
It is preferable that the value does not exceed 20, since this reduces air entrainment. In addition, from the viewpoint of shrinkage-reducing effect, co-adducts with an ethylene oxide/propylene oxide molar ratio in the range of 0 to 5 are preferable (especially pro-oxygen adducts), and in particular, those with only propylene oxide added are the most preferable. preferable. In this case, the scope of the present invention also includes those to which oxides such as butylene oxide and styrene oxide are co-added to an extent that does not impede the performance of the cement composition (usually 50% by weight or less based on the total oxyalkylene). .

Furthermore, in the general formula (1) of the present invention, (A O+n, (
The alkylene groups of A and A' represented by A'O-)-n' may be the same or different. When the amine compound has a primary amino group, this amino group may act as a monovalent to extend one chain of alkylene oxide, or act as a divalent to extend two chains, but in either of these cases. But that's fine. However, from the viewpoint of the shrinkage-reducing effect, a compound which acts as a divalent amino group and has an alkylene oxide added thereto is preferred, and is a compound in which m is 1 and l is 1 in the general formula (1). Further, when the amine compound is a polyamine, the amine group is preferably a residue that acts as a polyvalent and extends a large number of chains, and in this case as well, m is preferably 1 from the viewpoint of shrinkage reducing effect.

The method for synthesizing the compound of general formula (1) of the present invention involves adding an alkylene oxide to the amine compound, and then adding a polycarboxylic acid to the polycarboxylic acid so that at least one carboxyl group remains free. A method of esterifying to form an aminocarboxylic acid type compound is preferred because it is simple, but it is not limited to this method. Ammonia can also be esterified by reacting with polycarboxylic acid, then chloridizing the terminal hydroxyl group with phosphorus trichloride, reacting with isopropylamine, and then hydrolyzing in the presence of an alkali such as caustic soda. It can also be obtained by adding alkylene oxide to and then methylating with formic acid and formalin to obtain methyljetanolamine, which is then dehydrated and esterified by adding sodium monomaleate. When using acid-type compounds, the carboxylic acid group is usually used as a salt of alkali metals such as lithium, sodium, and potassium, alkaline earth metals such as calcium and magnesium, ammonia, and organic amines, but even in acid form, It can also be used in a partially neutralized form. Generally, it is preferable to use the sodium salt.

The shrinkage reducing agent for cement of the present invention can obtain an excellent shrinkage reducing effect by using one or a mixture of two or more compounds represented by the general formula (1) as an essential component. When a silicone surfactant is used in combination, the shrinkage reducing effect is further improved due to a synergistic effect, which is very preferable. There are cationic, nonionic, and anionic types of fluorosurfactants and silicone surfactants that are used in combination with these, and any of these can be used, but cationic,
A nonionic type is preferable from the viewpoint of reducing cement shrinkage, and a nonionic type is more preferable.

As the fluorosurfactant used in the present invention, commonly available commercially available ones can be used. A typical example of a cationic fluorosurfactant is a compound having a perfluoroalkyl group having 5 to 18 carbon atoms as a hydrophobic group, and a cationic hydrophilic group (for example, a quaternary ammonium base, etc.). There is. Examples include Florado FC-134 manufactured by Jusumari 3M Co., Ltd., Mega Fasoku F-150 manufactured by Dainippon Ink Chemical Co., Ltd.4, Surflon S-121 manufactured by Asahi Glass Co., Ltd., Sturgient 300 manufactured by Neos Corporation, etc. F-TOP EF--123B manufactured by Tohoku Fertilizer Company
, F-TOP EF-132, etc. A typical example of a nonionic fluorosurfactant is a carbon number 5.
There is a compound consisting of a perfluoroalkyl group of ~1 days as a hydrophobic group and a nonionic hydrophilic group (for example, an ethylene oxide adduct). For example, Florado PC-170C manufactured by Jujutsu 3M ■, Megafac F-142D, F-1440 manufactured by Dainippon Ink Chemical Co., Ltd.
, F--171, F-177, Freon S-141 manufactured by Asahi Glass Company, Sturgien manufactured by Neos Company) 200
．． 251, F-TOP EF-121 manufactured by Tohoku Fertilizer Company
, EF-122^, EF-122B, EF-12
2C, EF-122A3, etc. Typical examples of anionic fluorosurfactants include carbon atoms of 5 to
There is a compound consisting of a perfluoroalkyl group (18) as a hydrophobic group and an anionic hydrophilic group (for example, a sulfonic acid group, a carboxylic acid group, a phosphoric acid ester group, etc.).

This includes the Florado FC-9 manufactured by Jujutsu 3M ■.
5, FC-98, FC-126, FC-128, Mega Fasoku F-110, F-1 manufactured by Dainippon Ink Chemical Co., Ltd.
13, F-120, F-812, F-191.

Asahi Glass Surflon 5=tit, S-112,
S-113, Stargent 100 manufactured by Neos ■.

150, EF-TOP EF-102 manufactured by Tohoku Fertilizer Co., Ltd.
EF-103, EF-112, EF-123A,,
Examples include EF-123B. In addition to the above,
Cationic, anionic, and nonionic fluorosurfactants, Daikin Industries ■, Kanto Denka ■, Du Pont
, ICI, Hoechst % CIBΔ-GEI
It is also commercially available from GY companies, and these can also be used as the fluorosurfactant of the present invention.

In addition, the silicone surfactant used in the present invention has polysiloxane as a hydrophobic group, and a cationic hydrophilic group (e.g., quaternary ammonium base), a nonionic hydrophilic group (e.g., an alkylene oxide adduct), and a polysiloxane as a hydrophobic group. etc.), and an anionic hydrophilic group (for example, sulfate ester salt, phosphate ester salt, carboxylate salt, etc.). In Japan, various products are commercially available from Toray Silicone ■, Shin-Etsu Silicone, Toshiba Silicone ■, etc., and these various products can be used in the present invention.

The amount of shrinkage reducing agent used in the cement of the present invention is determined by the general formula (1
) It depends on the number of carbon atoms in the alkyl group and the number of carbon atoms in the alkylene group of the compound, but it is usually 0 for cement.
．． 5 to 10% by weight. If the amount used is less than 0.5% by weight, the effect of reducing shrinkage will be small, while if it exceeds 10% by weight, the strength of the cement composition will be about 2/2 that of one without additives.
3 or less, which is not sufficient for practical use. Further, when the compound represented by the general formula (1) and a fluorosurfactant or/and a silicone surfactant are used together, the shrinkage reducing effect increases due to a synergistic effect.

When these surfactants are used together, the amount of each compound added is 0.3 to 10% by weight of the compound represented by general formula (1) based on the cement weight, and the amount of the fluorosurfactant added is 0.3 to 10% by weight based on the cement weight. The amount of the silicone surfactant is 0.05 to 1% by weight based on the cement.

The means for adding the cement shrinkage reducing agent of the present invention is the same as in the case of cement admixtures that are generally used. For example, an appropriate amount of the cement shrinkage reducing agent is mixed in advance with kneading water, or cement, It is possible to adopt measures such as adding an appropriate amount of a cement shrinkage reducing agent during kneading of the mixture consisting of aggregate and water.

The cement shrinkage reducing agent of the present invention can be used in combination with other components (optional components).

Such optional ingredients include metal chlorides such as calcium chloride and sodium chloride, metal sulfates such as sodium sulfate, known cement hardening accelerators such as organic amines such as triethanolamine, alcohols, sugars, starch, and glycerin. , known cement hardening retardants such as sodium polyphosphate, known reinforcing steel rust preventive agents such as sodium nitrite and calcium nitrite, lignin sulfonic acid, oxycarboxylic acid, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate. Various cement dispersants, known cement dispersants such as carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, phosphorylated starch, and other cement thickening agents can be mentioned.

The method for constructing mortar or concrete to which the cement shrinkage reducing agent of the present invention has been added may be the same as conventional methods, such as applying with a trowel, filling a formwork, spraying, or pouring with a caulking gun. Further, the curing method may be any of air dry curing, humid air curing, water curing, heating accelerated curing (steam curing, autoclave curing, etc.), or these methods may be used in combination.

When the cement shrinkage reducing agent of the present invention is added to cement, a significant reduction in drying shrinkage is achieved compared to when no cement is added. In addition, it does not impair the nonflammability of the cement composition, and furthermore, it is possible to add a large amount (for example, about a few percent).
Even in this case, there is no significant decrease in the strength of the cement composition.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 After adding 8 moles of ethylene oxide to 1 mole of the amine compound shown in Table 1 by a conventional method, the mixture was reacted with 1 mole of maleic anhydride at 100 to 130°C for 2 hours to form a half ester of maleic anhydride. (Here, the half ester is one obtained by esterifying one of the two carboxyl groups of maleic anhydride and leaving the remaining one as a carboxylic acid group). The mixture was then neutralized with caustic soda to obtain the cement shrinkage reducing agent of the present invention. JIS A 1129 for cured mortar obtained by adding these shrinkage reducing agents in a pure proportion of 4.0% by weight to cement.
Shrinkage rate was measured using the dial gauge method of JIS R52.
The strength was measured using 01, and the results shown in Table 1 were obtained.

In addition, the amount of air is measured according to JIS A 112B.
Measured as concrete. In addition, in the case of mortar, the water/cement ratio is 65% and the sand/cement ratio is 200%. For concrete, unit cement amount is 300k
g/n? , the water/cement ratio is 60%, and the fine aggregate ratio is 44%.

Table 1 lists only the amine compounds constituting the X residue of general formula (1), which is the starting material for the cement shrinkage reducing agent. Or indicates that the test was performed on concrete.

Margin table below this page - 1 Example 2 Using butylamine and diethylenetriamine as starting materials as amines, changing the number of moles of alkylene oxide added,
Half-esterification was performed in the same manner as in Example 1 using 1 mole of maleic anhydride per mole of amine, and the mixture was neutralized with caustic soda to obtain various aminocarboxylic acid compounds. These were added in an amount of 4.0% by weight based on the cement, and the shrinkage rate, air content, and strength were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

In addition, EO in Table 2 represents ethylene oxide, and PO represents propylene oxide.

Margin table below this page - 2 (1) General formula (AO + n Contraction rate Mowing Q-4 air volume 28
day strength kgf/cn and +AO) rr part 28 days 91 days (%) Bending strength Compressive strength Starting material Nibutylamine 16 Eo 2 molar ratio 5.3
6.4 1.9 67 41617
EO4%7L 4.9 6.
0 1.8 71 42818 E
o 6 mole addition 4.7 6.1 1.5
73 4224 Eo 8 things t2I [I
4.5 6.0 1.6 7
2 '42119 1 mouthful of EO10 morui 5.0 6.4 2.0 6
8 40820 EO12 mono L→)ifu sword]
6.1 6.8 4.4
62 37221 EO14 Monoshii” Shiri mouth 6.5 7.4 7.8 5
5 33222 Eo 16 Mono L-JF Sword] 6.8 7.7 18.9
50 31623r504 mol, PO2 mol 4.8 5.8 1.4 72 416 addition 24E03 mol, PO3 mol 4.5 5.6
1.9 70 410e+11r+ Table-2 (2) Bi and K.

Isshin Toren - 匪 - Re: IEO Low ■ ■ F - RoF This page margin Example 3 Half esters were prepared by adding 6 moles of propylene oxide to 1 mole of butylamine and using 1 mole of various polycarboxylic acids. The aminocarboxylic acid compound is separated, neutralized, and added to cement as a sodium salt at 4.0% by weight.
Added. Note that when tricarballylic acid is used as the polycarboxylic acid, it is not a half ester, but one in which one of the three carboxylic acid groups is esterified. Polycarboxylic acids using anhydrides are esterified in the same manner as in Example 1, and when polycarboxylic acids other than anhydrides are used, they are reacted with dehydration at a temperature of 140 to 150°C. The esterification was completed when the acid value reached a predetermined value.

The shrinkage rate, air amount, and strength were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Margin table below this page-3 Margin below this page Example 4 Using the N112B cement shrinkage reducing agent of Example 2,
A test was conducted in the same manner as in Example 1 by changing the amount added, and the results shown in Table 4 were obtained.

Table 4 Margin below this page Example 5 2.5% by weight of the shrinkage reducing agent in Example 2, based on the cement, and 200 ppm of various fluorosurfactants based on the cement, or a silicone interface. The shrinkage rate, air content, and strength were measured in the same manner as in Example 1 using 0.1% by weight of the activator based on the cement, and the results shown in Table 5 were obtained. Table 5 also shows, as comparative examples, the results when a fluorosurfactant and a silicone surfactant were used alone, and when the shrinkage reducing agent of No. 28 was used alone.

Margins below this page Table 5 (1) Table 5 (2) qwa * Toray Silicone Surfactant Nonionic silicone surfactant Margins below this page Example 6 Shrinkage reducing agent positive of the present invention in Example 2 Example 1 was prepared by using 28 (2.5% by weight based on Mento, using Mega Fasoku F-1420 as a fluorosurfactant and S) 3747 as a silicone surfactant, and varying the amount of additive. The test was conducted in the same manner as above and the results shown in Table G-6 were obtained. In addition, Table 6 shows Megafupunk F-1420,S.
The results of tests using H3747 alone and varying the amount of (added) are also shown as comparative examples.

Margin table below this page - 6 (1) ■ 恁σ Margin table below this page - 6 (2) Procedural amendment writing method) % formula % 1. Indication of incident 1981 Tokuhoyo No. 231238 2. Name of invention Cement Relationship between Shrinkage Reducing Agent 3 and the Amendment Case Patent Applicant 4, Agent 8601-13 2m! 075-571
-1122 March 9, 1982 (March 29, 1982)
6. Subject of amendment March 18, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of the case 1983 Tokuhoyo No. 231238 2. Title of invention Shrinkage reducing agent for cement 3. Amendment Relationship with the patent applicant case Patent applicant 4, agent Tatami 601-13 11075-571-1
1226, Claim 1 subject to amendment, the following general formula (1) (wherein, X is an aliphatic amine having 1 to 7 carbon atoms;
7 cycloalkylamine or a residue obtained by removing (m+#) active hydrogens from a polyamine having 2 to 10 carbon atoms, A and A' are alkylene groups, and Y is a polycarboxylic acid obtained by removing two carboxyl groups. residue, (nXm×
If X is an aliphatic amine residue or a cycloalkyl amine residue, it is a number from 1 to 10, and when X is a polyamine residue, it is a number from 4 to 20, and m is a number from 1 to 4. number of l
is a number of 0-4, 0 is a number of 1 to 4, and M is an ion of hydrogen, alkali metal, alkaline earth metal, or ammonium. Reducer.

2. In the general formula (1), X is a residue of a primary aliphatic amine having 1 to 7 carbon atoms, m is 1, and β is 1. Shrinkage of the cement according to claim 1 Reducer.

3. In the general formula (1), X is a residue of an aliphatic amine having an alkyl group having 3 to 5 carbon atoms, m is 1, and β is 1, or The cement shrinkage reducing agent according to item 2.

4. In general formula (1), (nXm+×β) is 3 to
10. The cement shrinkage reducing agent according to claim 1, 2 or 3, wherein the cement shrinkage reducing agent is in the number 10.

5. In general formula (1), (AO+n and +A'
O) The cement shrinkage reducing agent according to claim 4, wherein the polyalkylene oxide represented by n' is a random or block adduct with an ethylene oxide/propylene oxide molar ratio of 0 to 5.

6. The cement shrinkage reducing agent according to any one of claims 1 to 5, wherein in general formula (1), Y is a dicarboxylic acid residue having 1 to 4 carbon atoms.

7. The cement shrinkage reducing agent according to claim 6, wherein the dicarboxylic acid is succinic acid, maleic acid, or fumaric acid.

8. A cement shrinkage reducing agent comprising an aminocarboxylic acid compound represented by the general formula (1) and a fluorosurfactant or/and a silicone surfactant.

91. The cement) O shrinkage reducing agent according to claim 8, wherein the fluorosurfactant and/or the silicone surfactant are cationic or nonionic surfactants.

10. The shrinkage reducing agent according to claim 8, wherein the fluorine-based surfactant and/or the silicone-based surfactant are nonionic surfactants.

Claims (1)

[Claims] l1 General formula (1) % formula % (1) (wherein, X is an aliphatic amine having 1 to 7 carbon atoms;
7 cycloalkylamine or a polyamine having 2 to 10 carbon atoms, each with (m+β) active hydrogens removed, A and A' are alkylene groups, and Y is a polycarboxylic acid with 2 carboxyl groups removed. residue, (nxm+rr
xl Ll: When X is an aliphatic heptamine residue or a cycloalkylamine residue, it is a number from 1 to 10, when X is a polyamine residue, it is a number from 4 to 2o, and m is a number from 1 to 4, l is a number from 0 to 4, 0 is a number from 1 to 4, and M is an ion of hydrogen, alkali metal, alkaline earth metal, or ammonium). Shrinkage reducing agent for cement. 2. In the general formula (1), X is a residue of a primary aliphatic amine having 1 to 7 carbon atoms, m is 1, and β is 1. Shrinkage of the cement according to claim 1 Reducer. 3. In the general formula (1), X is a residue of an aliphatic amine having an alkyl group having 3 to 5 carbon atoms, and m is 1,! The cement shrinkage reducing agent according to claim 1 or 2, wherein is 1. 4. In general formula (1), (nXm+×β) is 3 to
10. The cement shrinkage reducing agent according to claim 1, 2 or 3, wherein the cement shrinkage reducing agent is in the number 10. 5. In general formula (1), +AO)n and +A'0
) The cement shrinkage reducing agent according to claim 4, wherein the polyalkylene oxide represented by nj is a random or block adduct with a molar ratio of ethylene oxide/propylene oxide of θ to 5. 6. The cement shrinkage reducing agent according to any one of claims 1 to 5, wherein in general formula (1), Y is a dicarboxylic acid residue having 1 to 4 carbon atoms. 7. The cement shrinkage reducing agent according to claim 6, wherein the dicarboxylic acid is succinic acid, maleic acid, or fumaric acid. 8. A shrinkage reducing agent for cement 1, comprising an aminocarboxylic acid compound represented by the general formula (1) and a fluorosurfactant or/and a silicone surfactant. 9. The cement shrinkage reducing agent according to claim 8, wherein the fluorosurfactant and/or the silicone surfactant are cationic or nonionic surfactants. 10.7 The cement shrinkage reducing agent according to claim 8, wherein the sososurfactant and/or the silicone surfactant is a nonionic surfactant.