JPS59162164A - Cement dispersant composition - 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 a dispersion composition for use in cement that has excellent dispersibility, has little slump loss, and does not delay the hardening time of concrete.

Among the existing cement dispersants, salts of naphthalene sulfonic acid formalin condensate and salts of melamine sulfonic acid formalin condensate have superior cement dispersion ability, and are therefore characterized by the ability to significantly reduce the amount of concrete mixing water. Conch requires high strength! J-1-Used in large quantities in secondary products. However, salts of naphthalene sulfonic acid formalin condensate and salts of melamine sulfonic acid formalin condensate give concrete with excellent fluidity immediately after being mixed with cement, bone stone, water, etc., but after mixing, The disadvantage is that the fluidity decreases rapidly over time.This decrease in fluidity is called a slump loss, and because of this slump loss;
It has the disadvantage that it is difficult to use for ready-mixed concrete, which requires no major slump loss to occur within 5 hours. In order to improve the slump loss, a method was devised to adjust the timing of addition of the salt of naphthalene sulfonic acid formalin condensate, for example, a method of adding it after cement 1- was hydrated by contact with water (Japanese Patent Publication No. 51-15
856 Special Publication No. 53-5691, Special Publication No. 53-5692
) has a very satisfactory effect, but has the disadvantage that the addition method is complicated. On the other hand, it is known that the initial water use of cement is responsible for the increase in slump loss of concrete using naphthalene sulfonate formalin ld compound salts and melamine sulfonate formalin condensate salts. Therefore, in order to reduce slump loss, cement retarders are used in combination. These setting retarders include ligninsulfonic acid and nitrofumic acid.

Organic compounds such as gluconic acid and inorganic compounds such as sodium 1-ribolyphosphate are known. However, if these retarders are used in combination, the curing time of concrete will be delayed. Demoulding of concrete is usually carried out within 1 to 3 days after concrete is poured, and therefore early strength (strength after 1 to 3 days) is very important, but the above-mentioned setting Naturally, when a retardant is used in combination, this early strength is difficult to increase. For this reason, in the summer when concrete hardens very quickly, 1 can be used with a setting retarder, but in the spring and autumn when concrete 1 does not harden so quickly (rll pear-shaped time needs to be increased). It has the disadvantage that it is difficult to use, especially in the winter when concrete hardens slowly (in fact, it cannot be used at all).

Under these circumstances, the present inventors have conducted intensive studies on dispersion compositions for use in cement that have excellent cement dispersion ability, do not delay cement hardening, and have little slump loss, and as a result, have arrived at the present invention. Ta. That is, the present invention is a cement 1-dispersed composition characterized by comprising the following two components (c) and [F]).

(f) Salt of naphthalene sulfonic acid formalin condensate and/or salt of melamine sulfonic acid formalin condensate 9
5 to 50 parts by weight G3) The molar ratio of the structural unit represented by the following general formula (D) to the structural unit represented by the general formula (A) is 9/1 to 1/9
5 to 50 parts by weight of a water-soluble polymer compound with a molecular weight of 1,000 to 50,000 within the range of
is an alkylene group having 2 to 3 carbon atoms, n is 0 or 11m1
is a number from 0 to 20) (In the formula, R2 and R3 are hydrogen or a methyl group, and xo is hydrogen or a salt.) In the present invention, the salt of a naphthalene sulfonic acid formalin condensate is a highly formalin condensate of naphthalene sulfonic acid. The condensed product is neutralized with caustic soda, calcium hydroxide, etc. For example, Japanese Patent Publication No. 41-11737.
Those listed in Japanese Patent Publication No. 48-9564 may be used. There are naphthalene sulfonic acid, α-naphthalene sulfonic acid, β-naphthalene sulfonic acid, and β-naphthalene sulfonic acid is preferred. In addition, in the present invention, the naphthalene sulfonic acid formalin condensate salt may include other aromatic compounds and/or these sulfones, in addition to the naphthalene sulfonic acid formalin condensate salt, as long as the performance is not impaired. It also includes those co-condensed with acids. Examples of these include JP-A-51-17219. Tokukai 1975
-29644. Examples include those described in Japanese Patent Application Laid-Open No. 50-58120, and various other materials.

Examples of these are aromatic compounds such as naphthalene and anthracene; aromatic sulfonic acids such as benzenesulfonic acid, anthracene sulfonic acid; toluenesulfonic acid, dodecylbenzenesulfonic acid, methylnaphthalenesulfonic acid, ethylnaphthalenesulfonic acid; A wide variety of alkyl-substituted aromatic sulfonic acids; alkoxy-substituted benzene sulfonic acids such as methoxytetrabenzene sulfonic acid; hydroxy-substituted benzene sulfonic acids such as phenolsulfonic acid; Examples include yohyalkoxy-substituted benzene sulfonic acid; alkyl-substituted benzene sulfonic acid such as creso-7resulfone 1'-tane; and the like. The proportion of these naphthalene sulfonic acids and other aromatic compounds and/or these aromatic sulfonic acids that are co-condensed to an extent that does not impair their performance is generally 30 parts by weight or less per 100 parts by weight of naphthalene sulfone e.

In addition, as the salt of the naphthalene sulfonic acid formalin condensate used in the present invention, sodium salts are usually used, but in addition to these, alkali metal salts such as lithium salts and potassium salts, and calcium salts are also used.

Salts of divalent metals such as magnesium, zinc salts, and iron salts,
a! It can also be used as one of trivalent metals such as reminium salts and iron salts, as well as ammonium salts. Organic amine salts and alkanolamines may also be used, and two or more of these various salts may be used in combination.

In addition, the salt of melamine sulfonic acid formalin condensate used as the component (f) of the present invention is melamine sulfonic acid/formalin condensate.
It is a salt obtained by condensing with formalin, and any commercially available salts may be used. For example, the Me/Reme Nt manufactured by Showa Denko K.K., NL-4000 and NP-20 manufactured by Hozorisu Bussan.
etc. fall under this category. The salt of this melamine sulfonic acid formalin condensate is generally melamine and formaldehyde or paraforma/redehyde, sulfite (sodium sulfite,
ammonium sulfite, sodium bisulfite, ammonium bisulfite, etc.) in water under alkaline conditions (e.g. pH
9 to 12), or under alkaline conditions, further under weak acidity (for example, p
H4-6) or additively reacted under alkaline conditions under strong acidity (e.g. pH
Examples include those in which the high Kkli is combined in 2 to 4). Among these, those that are highly condensed under strong acidity are more preferable than cement dispersibility. Furthermore, among the salts of naphthalene sulfonic acid formalin condensate and the salts of melamine sulfonic acid formalin condensate used as components of the present invention, the salt of naphthalene sulfonic acid formalin condensate is more preferable than the cement l-dispersing ability. It is.

Water-soluble polymer compound U, which is component 0 of the present invention, has the general formula [
Power on the side chain indicated by )! Hydroxyl-g'i in the structural unit having levoxy/L[' and the side chain represented by general formula (I)
C-(CH2)n-0-(AO)mH]
has. ; It is a copolymer consisting of a structural unit. Such polymer compounds are usually produced by copolymerizing a monomer having a carboxy)V group and a monomer having a hydroxyl group in a predetermined ratio by radical/I/polymerization, ionic polymerization, photopolymerization, radiation polymerization, etc. obtained by Examples of monomers having a carboxyl group that provide the structural unit of general formula ([) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid. In addition, examples of monomers having a hydroxyl group in the present invention include ali)) real alcohol, real alcohol,
Examples include unsaturated alcohols such as alcohols, alcohols, and adducts of ethylene oxide and/or propylene oxide with these alcohols.In this case, additions of ethylene oxide and propylene oxide It indicates the number of moles.If m in the general formula (〇) exceeds 20, it is not preferable because a very large amount of air will be entrained in the concrete and the strength of the concrete will decrease. Component (1) of the present invention can be obtained by various methods other than the above-mentioned copolymerization of a monomer having a carboxy group and a monomer having a hydroxyl group. For example, it may be obtained by copolymerizing a monomer having a carboxyl group and the unsaturated alcohol/I/s, and then adding a predetermined amount of ethylene oxide or/and propylene oxide (in this case, carboxylic acid/ The L/ group should be in the carboxylic acid form or salt form). Alternatively, the monomer having a carboxyl group may be copolymerized with vinyl esters such as vinyl acetate and vinyl propionate, and then hydrolyzed. Alternatively, after the hydrolysis, a predetermined amount of ethylene oxide or and propylene oxide, which may be obtained by total addition (even in this case, the carboxyl group is kept in the form of carboxylic acid or salt). Among these various water-soluble polymer compounds (1) having carboxyl groups and hydroxyl groups, compounds in which R2 is hydrogen and R3 is hydrogen or a methyl group are preferred for their slump loss improvement effect and cement dispersion ability. It is manufactured from acrylic acid and methacrylic acid, which provide structural units. Particularly preferred are acrylic acid, methacrylic acid, and the general formula (Al giving a structural unit in which R1 in D is hydrogen or a methyl group, n is 1, and m is a number from 0 to 5)) real alcohol, crotyl a) V :I-
) or a copolymer with allyl alcohol propylene oxide adduct. In addition, in component (2) of the present invention, the structural unit represented by the general formula (r) and the general formula (I[
It is essential that the molar ratio of the structural units represented by ) is within the range of 9/1 to 1/9. If this ratio exceeds 9/1, the effect of improving slump loss will not only be reduced, but also the curing of concrete will be delayed to some extent.9, and if this ratio is less than 1/9, there will be almost no effect of improving slump loss, which is undesirable. In particular, it is preferable that this ratio is 7/3 to 3/7, 11 (α pronation, because it has the greatest effect of improving slump loss and has excellent cement dispersion ability (but is excellent and does not delay the hardening of cement at all. In the present invention, the polymer compound (containing the above-mentioned carboxyl hydroxyl groups in a predetermined proportion), which is component You can also use things.

Examples of these other unsaturated monomers include acrylic acid esters, esters such as methacrylic acid esters (the number of carbon atoms in the ester moiety is 20 or less), vinyl acetate, propionic acid esters, and vinyl esters such as propionic acid esters and methacrylic acid esters. Examples include various esters such as vinyl aromatics such as styrene, sulfonic acids such as styrene sulfonic acid and vinyl sulfonic acid, and olefins such as butene, isobutyne, and octene. Copolymerization of acrylic esters, methacrylic acid esters, styrene sulfonic acids, etc., in which the number of carbon atoms in the ester group is 4 or less, can sometimes give favorable results in terms of cement dispersion ability. The amount of these other unsaturated monomers added varies depending on the type of hydroxyl group or carboxyl group in the component, or their equivalent ratio, but is usually 30% by weight or less.

Such a water-soluble polymer compound (2) can be obtained according to a method commonly used in industry. For example, radical polymerization is common as a form of reaction, and solution polymerization is preferred in this case. Hydrocarbons such as esters, hydrocarbons such as Hensen, and ketones such as aceline and methyl ethyl N-ketone are used as solvents. Polymerization initiators include peroxides such as benzoyl peroxide and tert-butyl peroxide, azo compounds such as azobisisobutyronitrile, and even persulfates, depending on the type of solvent and the type of polymer. The activation energy for decomposition is small, so polymerization can be initiated under mild conditions. The copolymer obtained in this way can be used as component (1) of the present invention even if it is diluted with an acid, but it can be neutralized with an alkali substance, and it can be used as an alkali metal salt such as lithium, sulfurium, potassium, calcium, magnesium, etc. Alkaline earth metal salts such as aluminum can be formed. Molecular weight (・ma, monomer concentration in the solvent.

It can be adjusted by changing the reaction temperature and reaction time, but
Those having a molecular weight in the range of 1,000 to 50,000 have particularly good water solubility and exhibit remarkable dispersibility in cement. If it is less than 1000, slump loss becomes large and setting delay occurs. If it exceeds 50,000, the water-reducing performance of the salt of the naphthalene sulfonic acid formalin condensate will decrease and the slump loss will increase. More preferably, the molecular weight is in the range of 3,000 to 30,000.

Before, ir! It is necessary that the pure ratio of (f) (i) is 95 to 50 parts by weight of component ~ and 5 to 50 parts by weight of component @). (2) When the component is less than 5 parts by weight, the effect of improving slump loss is small and when it exceeds 50 parts by weight, the slump loss becomes large.

Preferably (f) component 90 to 60 parts by weight, (f) component 1
0-40, more preferably (g) 90-70. (13)1
The amount is 0 to 30 parts by weight.

In addition to fA) and (B), other components (optional components) can be added as necessary. With such optional ingredients
t'j, , 7 /L/Known cement dispersants such as killbense sulfone sulfonic acid and boria llechlene gellicol; calcium chloride, sodium chloride, sodium sulfate, charcoal 1'<2 soda, potassium carbonate, thiosulfuric acid Known cement hardening accelerators such as sodium and alkanolamines; Known cement hardening retarders such as lignin sulfonic acid, gluconic acid, citric acid, tartaric acid, and polyphosphoric acid; Various substances can be added, such as known glue agents such as Rerose and hydroxymethylcellulose; known rust preventive agents such as sodium nitrite and calcium nitrite.

Cement that can be used in the dispersion composition of the present invention include ordinary Portland cement cement, moderate heat Portland cement, alumina cement, fly ash cement, blast furnace cement 1, and the like. Among these, preferred is Portland cement.

The amount of the dispersion composition of the present invention to be added depends on the use of cement.

Although various changes can be made depending on the required performance, the dispersion composition of the present invention is usually used in cement with a pure content of 0.01%.
-5% by weight, preferably 01-1% by weight. For ready-mixed concrete, usually Q1~05 double fluorescent %,
In the case of two-shot concrete products, it is usually 0.3 to 1% by weight.

This dispersion composition is usually added when mixing cement and aggregate (sand, crushed stone, etc.) and adding mixing water.
It may be added after kneading bone paulownia and water and after the cement is hydrated by contact (1 to 2 minutes after kneading), or it may be added to cement in advance and then water is added. Alternatively, a divided addition method may be used in which a part of the present dispersion composition is added during kneading and kneading, and then the remaining present dispersion composition is added in one or more divided portions. Moreover, the composition of the present invention 'f: J! Even if you add each component separately to cement, aggregate, water, etc. and knead it, or add each component separately at various stages of the cement mortar or concrete mixing process, the final mixture can be mixed. Since the effects of the present invention can be obtained if the composition of the present invention is produced in the product, such a method can also be used.

The method for constructing mortar and concrete containing the dispersion composition of the present invention may be the same as conventional methods, and various methods may be used, such as troweling, spraying, filling into formwork, and injection with a caulking gun. In addition, curing methods include air dry curing, humid air curing, and water curing.

Either heating accelerated curing (steam curing, autoclave curing, etc.) may be used, or a combination of each may be used.

The dispersion composition of the present invention has excellent cement dispersion ability, and is characterized by not slowing cement hardening and having little slump loss. Taking advantage of this characteristic, the present dispersion composition is used for mortar and concrete for decking, walls, and floors; waterproof mortar, waterproof concrete, 1Jμ structures of buildings, and molded parts of buildings, and is especially suitable for slump loss. Ready-mixed concrete is used for the framework of buildings due to its low
1. A mortar for producing secondary concrete products due to its excellent dispersibility.

Suitable as a dispersion composition for concrete.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. Note that all parts in the examples indicate parts by weight based on pure components.

Example 1 (iii) 75 parts of a naphthalene sulfonic acid formalin condensate (3-') rambana (hereinafter abbreviated as NSF).

Component (B) is obtained by copolymerizing 50 mol% of aryl alcohol or an alkylene oxide adduct of aryl alcohol with 50 mol% of a monomer having various carboxy/silicone groups. Molecular weight: 000~
A composition of the present invention was obtained using 25 parts of a 11um salt of a water-soluble polymer compound of 10,000. Also vinyl acetate/115
A water-soluble polymer compound with a molecular weight of 8,000 obtained by copolymerizing 0 mol% and 50 mol% of acrylic acid was saponified with sodium methylate, and by-products such as methyl acetate were removed (!
Component 3) was also used to obtain the composition of the present invention. Using these, the following concrete mixtures were prepared and the slump loss, setting time and strength of the concrete were measured, and the results shown in Table 1 were obtained. In addition, in Table 1, for comparison with the composition of the present invention, NSF is used when NSF alone is used, NSF is used in combination with NSF and sodium gluconate, which is a setting retarder; When 50 mol% maleic anhydride and 50 mol% isobutyne copolymer soda salt were used together, when a lignin-based commercially available water reducer (Bozolis N05L, standard type) was used, and when no dispersant was used at all. The results are also listed. In addition, the mix of concrete is 0.20% of the dispersion composition (11 cement,
purity%).

The unit cement amount is 320 kg ATLI', the water/cement ratio is 55%, and the bone ratio is 46%.The concrete mix when no dispersant is used is 9/'In for the unit cement amount 320. ” r Water/cement ratio 60%
, the fine aggregate ratio is 46%, and the concrete temperature is 20%.
°C, the compressive strength is the value of 1@ when cured in water at 20 °C.

In addition, in Table 1, ALA means allyl alcohol,
ALAEOL. am 3. Q+ 5-0 + tQ r
2Q i PO2- G) 5-Q is each one of allyl alcohol-propylene oxide. . z 3. O, Ha O
) 10,20y 3" Ojs.o monolay 4 added. VAC indicates vinyl acetate tVk saponified after copolymerization.

(*) Slump loss amount refers to the slump immediately after kneading and the 30
This is the difference between the slump after 1 minute, 60 minutes, and 90 minutes.

The larger this value is, the more likely it is that the fluidity of concrete is decreasing.

As is clear from Table 1, the product of the present invention has significantly improved slump loss compared to the case of NSF single worm, and is also superior to the lignin-based water reducing agent commonly used in Retemix 1-Concrete 1-. Even when compared, the slump loss (is less. Furthermore, what is noteworthy about the November product is not only that the slump loss is less, but also that the slump loss is less.
2. Concrete hardening is not delayed. What is the invented product? There is no strange delay in dispersion (because there is no such thing, it is sufficiently large to meet the standard water reducing agent standards set by the Architectural Institute of Japan). No more than 1 early, no more than 1 hour and 30 minutes late4
Those that do not have a standard type are defined as standard types. ) On the other hand, when sodium gluconate, which is a conventional technique, is used in combination, the slump loss is reduced (V), but the hardening of the concrete is delayed by a long time, and early strength (1 day with the bowworm I button) is reduced.
It can be seen that it cannot be used practically in spring, autumn, and winter 1υ1.

Example 2 75 parts of sodium salt of melamine sulfonic acid formalin condensate (hereinafter abbreviated as MSF) as component (c), [F]
50 mol% of an alkylene oxide adduct of allyl alcohol or allyl aurco-)V as a component) and 50 mol% of a monomer having various carboxy)V groups with a molecular weight of 5oooo to 10,000. A composition of the present invention was obtained using 25 parts of rum salt of the water-soluble polymer compound 1-1. Using these, various Funkrete tests were carried out in the same manner as in Example 1, and the results shown in Table 2 were obtained.
2 also includes the results obtained when MSF was used alone for comparison.

Example 3 Cement dispersion using 75 parts of N5F as the (f) component and 25 parts of a sodium salt of a water-soluble polymer compound with a molecular weight of 1000 to 100 OO obtained by changing the copolymerization composition of acrylic acid and ALA EO, and o as the component (2). It was made into a composition. Using these, each seeding concrete 1.
Try! After being frugal, we obtained the results shown in Table 3.

Example 4 Using NSF as the component, acrylic acid 5 as the component
0 mole% and ALA Eol, o! A cement dispersion composition was obtained by using 50 mol % of a sodium salt of a copolymer having a molecular weight of 8,000 and changing the mixing ratio of the components.

Using these, various concrete tests were performed in the same manner as in Example 1, and the results shown in Table 4 were obtained.

As is clear from the above table, if the amount of component (2) is too small, there is no effect of improving the slump loss, and if the amount of component (2) exceeds 50%, the slump loss becomes large.

Example 5 (1) 75 parts of NSF as a component, but 50 mol% of acrylic acid and allyl alcohol as components.
Using 25 parts of sodium salts of copolymers with different molecular weights of 50% to 1%, each oak concrete test was conducted in the same manner as in Example 1, and the results shown in Table 5 were obtained.

Claims (1)

[Claims] 1. A cement dispersion composition with low slump loss, characterized by comprising the following two components (g) and CB). ■ Salt of naphthalene sulfonic acid formalin condensate and/or salt of melamine sulfonic acid formalin condensate 95
~50 parts by weight (to) the structural unit represented by the following general formula (I) and the general formula [
5 to 50 parts by weight of a water-soluble polymer compound with a molecular weight of 1,000 to 50,000, in which the molar ratio of structural units represented by A phenyl group
is an alkylene group having 2 to 3 carbon atoms, n&j: 0 or 1.
(wherein, R2 and R3 represent hydrogen or a methyl group, and Xl represents hydrogen or a salt) according to item 1, wherein component 2 is a salt of a naphthalene sulfonic acid formalin condensate. Dispersion composition. (a) The dispersion composition according to item 1 or 2, wherein the molar ratio of the structural unit represented by general formula (I) to the structural unit represented by general formula Nail is within the range of 773 to 3/7. 4. The dispersion composition according to any one of Items 1, 2, and 3, wherein R2 in the general formula (to) is hydrogen or R3 is hydrogen or a methyl group. 5. R1 in general formula (I) is hydrogen or a methyl group, and n is l. The first term, second term, and third term are because lη is 0 to 5. The dispersion composition according to any one of Item 4. Item 1, in which the molecular weight of the component (a) is 3,000 to 30,000. The dispersion composition according to any one of Items 2, 3, 4, and 5.