PatentDe  


Dokumentenidentifikation EP0515529 04.01.1996
EP-Veröffentlichungsnummer 0515529
Titel FLIESSFÄHIGKEIT VERBESSERNDES MITTEL, VERFAHREN ZU SEINER HERSTELLUNG UND SEINE VERWENDUNG.
Anmelder Perstorp AB, Perstorp, SE
Erfinder OLSSON, Lars-Inge, S-252 33 Helsingborg, SE;
HAMACEK, Kent, S-284 00 Perstorp, SE
Vertreter Hoffmann, Eitle & Partner Patent- und Rechtsanwälte, 81925 München
DE-Aktenzeichen 69114831
Vertragsstaaten AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, LI, LU, NL, SE
Sprache des Dokument En
EP-Anmeldetag 12.02.1991
EP-Aktenzeichen 919049445
WO-Anmeldetag 12.02.1991
PCT-Aktenzeichen SE9100096
WO-Veröffentlichungsnummer 9112214
WO-Veröffentlichungsdatum 22.08.1991
EP-Offenlegungsdatum 02.12.1992
EP date of grant 22.11.1995
Veröffentlichungstag im Patentblatt 04.01.1996
IPC-Hauptklasse C04B 24/22
IPC-Nebenklasse C04B 24/06   

Beschreibung[en]

The present invention relates to a flowability improving agent which also gives a prolonged workability time of an aqueous cement containing composition, a process for the production of such an agent and a use thereof.

Flowability improving agents have been known for a long time as additives to compositions containing cement, lime and/or gypsum. Grouts, mortars, concrete, putty and self levelling floor screeds constitute examples of cement based mixtures. Usually these mixtures are composed in such a way that they contain a surplus of water as compared to the miminum amount necessary for the curing or binding reaction of the cement.

If you tried to use exactly the amount of water necessary for the curing, the mixture would get an unsatisfactory consistency and workability due to the strong attractive forces between the cement particles.

On the other hand, a too high water content in the mixture mentioned results in a drastic decrease of the strength of the cured mixture. However, to a certain extent this can be compensated by an increase of the cement content at the composition of the mixture. A too high content of cement per unit of volume has, however, the negative effect that the heat release at the curing reaction may result in crack formations and other less desirable effects. Also from an economical viewpoint it is undesirable with a higher content of cement than necessary.

Nowadays, cement based mixtures are often pumped under pressure through a pipeline at the use on the different building work sites. Then it is important that the mixture has a pumpable consitency but not a too high water content.

It is known before to use certain concrete additives to be able to decrease the water content of the concrete mixture and at the same time get a good flowability. The most known of these additives are sulphonated naphtalene-formaldehyde resins, sulphonated melamine-formaldehyde resins, sulphonated melamine-urea-formaldehyde resins and sodium and calcium salts of ligninsulphonic acid.

Thus, these known additives give a certain effect in the respects mentioned above.

The conception of workability time is used in the present technical field to define the period of time after mixing a flowability improving agent of the above mentioned type with a concrete mixture, during which the mixture has a better flowability than the corresponding concrete mixture without any admixture of a flowability improving agent.

Different methods can be used to determine the workability time. According to the present patent application a standardized Swedish method, SS 137121 is used for consistency measuring. Then a metal cone is filled with a concrete mixture whereupon the cone is lifted up and taken away. Then the concrete cone sinks down.

The difference between the height of the concrete cone and the metal cone, the so-called slump is used as a measure of the consistency of the concrete. Then the slump is measured on a concrete mixture before the admixture of a flowability improving agent and after the admixture thereof. Samples are taken out at even intervals until the slump of the concrete mixture containing the flowability improving agent has reached the same value as the concrete mixture had before the addition of the agent. The time period measured constitutes the workability time.

Todays concrete producers and building contractors often have very big problems with too short workability time of the concrete. Thus, the effect of the flowability improving agent in the concrete decreases too quickly. Sometimes for instance the transport of the concrete from the concrete factories to the building sites takes too long time for allowing the concrete to fill the moulds etc before it loses its flowability. Moreover, on the building site pouring stops can occur of different reasons. When the pouring then starts again the conrete has lost a great deal of its workability. This causes big problems especially at pumping of flow concrete. A plugged pump conduit can result in very big economic consequences.

The problems with too short workability time are particularly big at high concrete temperatures during summer time and at pouring with warm concrete during winter time.

Of the above flowability improving agents, above all sulphonated melamine-formaldehyde resins and sulphonated naphtalene-formaldehyde resins are used for flow concrete. Then the problems disclosed above occur.

Very big research efforts have been spent in many places in the world to solve the problem with too short a workability time of concrete. In certain cases it has partially been possible to extend the workability time. However, at the same time other problems have appeared, such as a decreased short time strength, an increased air content, a risk of false set or an extremely prolonged time of initial setting of the concrete. These problems are so serious per se that it cannot be said that the problem with a short workability time has been solved in a satisfactory way before.

According to the present invention it has now been possible to solve the above problem with a short workability time without the appearance of the other problems mentioned.

Thus, the invention relates to a flowability improving agent which also gives a prolonged workability time of a cement containing aqueous composition. Calculated on a dry product the agent comprises a combination of

  • A) 60-99 % by weight of sulphonated melamine-formaldehyde resins, a sulphonated melamine-urea-formaldehyde resin or a sulphonated naphthalene-formaldehyde resin.
  • C) 0.5-40 % by weight of a boron containing polyhydroxy carboxylic acid or a watersoluble alkali salt or alkaline earth metal salt of such an acid which per se has got the formula
    where R&sub1; is
    and n is 3-8, preferably 4-6 and possibly
  • D) 0.5-30 % by weight of a compound with the general formula



    Ar O - [R&sub1;]n - R&sub2;



    where Ar is a possibly substituted benzene rest or naphtalene rest, R&sub1; is an oxyethylene group;

    - CH&sub2;CH&sub2;O - or an oxypropylene group;
    an oxyethylene chain or an oxypropylene chain with up to fifteen oxyethylene groups or oxypropylene groups or a combination of oxyethylene groups and oxypropylene groups to a chain where the sum of these groups is at most fifteen; the mean value n for n is 1-15 and R&sub2; is hydrogen or a phosphonate group with the formula
    where M&sub1; and M&sub2; are hydrogen ion or alkali metal ion or where R&sub2; is a group with the formula
    where M&sub2; has the above meaning and M&sub3; is - [R&sub1;]n - O Ar

    where R&sub1;, n and Ar have the above meaning.

The compound A) of the flowability improving agent can be produced in many different ways. One suitable method is shown in the Swedish patent 7414830-5, which discloses sulphonated melamine-formaldehyde resins. The commercial product Melment L-10 sold in Sweden by Cementa under the name Cementa flow additive V 33 as well as the products PERAMIN F® and PERAMIN FP®, both sold by Perstorp AB, can be used as component A) according to the present invention.

The published Japanese patent application 57-100959 also relates to production of sulphonated melamine-formaldehyde resins. Said process can be used too at the production of the component A) above.

Furthermore, the U.S. patent 2,730,516, the Austrian patent 263,607 and the European patent 59,353 can be mentioned. They also relate to the production of sulphonated melamine-formaldehyde resins.

Sulphonated naphtalene-formaldehyde resins are also commercially available for instance from the French company Compagnie Francaise De Produits Industriels.

According to a preferred embodiment of the invention, R&sub1; in the compound D) is an oxyethylene group and n is 1-6.

In another preferred embodiment of the invention, R&sub1; in the compound D) consists of an oxypropylene group, whereby n is 3-8.

Ar in the compound D) is preferably a benzene rest and R&sub2; is a phosphonate group with the formula

where M&sub1; and M&sub2; are hydrogen ion or alkali metal ion.

It is very suitable to use a sulphonated melamine-formaldehyde resin or a sulphonated melamine-urea-formaldehyde resin as compound A).

If Ar in the compound D) is substituted with an alkyl group this should preferably consist of short chains, such as CH&sub3;, C&sub2;H&sub5; or C&sub3;H&sub7;.

A flowability improving agent consisting of a combination of the compounds A) and D) above is disclosed before in the Swedish patent 8800295-1. The agent according to said patent has a tremendously good flowability improving effect on concrete for instance. However, the workability time of concrete mixtures containing that flowability improving agent is not satisfactory at certain applications. Accordingly you get the problems mentioned above.

In the present technical field the time of initial setting is usually defined as the time period needed after the mixing of the concrete to allow the concrete to cure to such an extent that it can be flattened for instance. Of course usually a long time of initial setting of a concrete mixture is very unfavourable. Then the work has to be stopped for a long time while you are waiting for the concrete to cure. The initial setting time can be measured in different ways.

In the present patent application it is measured according to the Swedish standard SS 137126. Then stamps are used which are pushed into the concrete at different moments. The resistance against penetration is measured. The limit for the end of the time of initial setting according to this standard is the point of time when the resistance against penetration has reached 3.5 MPa.

A high short time strength of concrete is important from different points of view. Above all it is important to make it possible to demould as quick as possible. In the embodiment examples below the short time strength has been defined as the 24 hours compression strength.

According to the U.K. patent 1.389.407 it is known before to produce one embodiment of a compound C) of the present invention. No use of the known compound is mentioned in that U.K. patent.

In the U.S. patent 3.856.541 a concrete mixture containing a component C) of the present invention is disclosed. However, no combination with our other components is shown in this patent which relates to a prolongation of the time of initial setting of the concrete to prevent it from curing so quickly at the high temperature used (200oF≈93oC). The problem with the workability time is not discussed at all in this U.S. patent.

Accordingly the compound C) has not been used before to prolong the workability time of concrete mixtures and the like.

Concrete mixtures containing compound A only do not give the prolonged workability time according to the present invention. The same thing is true for a combination of the compounds A and D as mentioned above.

Thus, the present invention solves a totally different problem than that according to the patents disclosed above.

It is very surprising that a flowability improving agent can be brought about according to the present invention, which agent gives a good flowability improving effect as well as a prolonged workability time of an aqueous composition containing cement by a combination of the components A) and C) and possibly D).The component C) does not give any prolonged workability time. Moreover, component A) does not give any prolonged workability time but only a good flowability improving effect.

Calculated on a dry product the agent according to the invention suitably consists of 70-99 % by weight, preferably 80-99 % by weight of compound A, 0.5-30 % by weight, preferably 0.5-20 % by weight of component C) and possibly 0.5-20 % by weight of compound D).

According to one preferred embodiment of the invention the agent consists of 70-99 % by weight of compound A), 0.5-20 % by weight of compound C), 0.5-20 % by weight of compound D) calculated on a dry product.

At another much preferred embodiment of the invention the agent consists of 70-99 % by weight of compound A) and 0.5-30 % by weight of compound C) calculated on a dry product.

In the formula of the compound C), n is preferably 5.

The boron in the compound C) is often present as a complex. The formulas of a few such complexes included in the present invention are shown in the U.K. patent 1.389.407 mentioned above.

According to one embodiment of the invention the component C¹) consisting of boric acid or a water-soluble salt of boric acid and C²) a polyhydroxy carboxylic acid or a water-soluble alkali salt or an alkaline earth metal salt of such an acid having the formula

where R&sub1; is

and n is 3-8, preferably 4-6, which partial components C¹) and C²) have been mixed with the other components present in the agent.

At one suitable process for the production of the flowability improving agent according to the invention the compound C¹) above is added at the production of a sulphonated melamine-formaldehyde resin or a sulphonated melamine-urea-formaldehyde resins A).

Usually, an acid reaction step is included at the production of such resins. There the low pH value is brought about by means of an acid catalyst, for example consisting of an inorganic acid such as sulphuric acid, an organic acid or another acid compound.

Advantageously, the compound C¹) can be added at said step, especially if the compound consists of boric acid. The boric acid can work as an acid catalyst and then wholly or partly replace the above catalysts, which are usual in this connection.

However, the components C¹) and C²) can also be added at another step of the production of the resin A).

An addition of the components C¹) and C²) in more than one step is also possible. The components C¹) and C²) can be added to a finished resin A) too.

Possibly also component D) is admixed at this process as mentioned above.

Of course the agent according to the present invention can be produced in other ways within the scope of the invention. Thus, the components A and C and possibly D can be mixed together in any order. The different partial components of the agent can also be added separately to a cement containing composition and then be carefully mixed with it.

The agent can be present as an aqueous solution or as a dry product. Suitably the dry product is produced by spray drying of a corresponding aqueous solution.

Preferably, the aqueous composition containing cement consists of concrete, self levelling floor screeds, grouts and mortars.

The agent according to the invention can also be used for decreasing the water content of the concrete mixture and at the same time give a good flowability and a prolonged workability time of the mixture.

The present invention will be explained more in detail in connection with the embodiment examples below, of which examples 2, 7, 8 and 9 illustrate the use of an agent according to the invention, while examples 1, 3, 4, 5 and 6 relate to comparison tests outside the scope of the invention.

Example 1

A concrete composition was produced by mixing for 2 minutes

290 kg/m³ cement (Slite standard Portland)

1063 kg/m³ dry gravel, 0-8 mm

730 kg/m³ coarse gravel, 8-16 mm

228 kg/m³ water

Directly after the production the concrete mixture had a slump of 80 mm measured according to the above method.

Thereafter, 3.8 kg/m³ (1.3 % by weight of the cement) of a sulphonated melamine-formaldehyde resin PERAMIN F® (component A) from Perstorp AB was admixed for 2 minutes.

Directly after the admixture of the sulphonated melamine-formaldehyde resin the concrete mixture had a slump of 220 mm. Then the slump was measured with an interval of 20 minutes. The following values were obtained. Slump, mm after 20 min 195 after 40 min 130 after 60 min 100 after 80 min 80

Thus, 80 minutes after the admixture of the resin the slump of the concrete mixture had decreased from 220 to the value 80 it had got before the addition of the resin. Accordingly the workability time measured according to the definition disclosed above was 80 minutes.

Test specimens made of the concrete mixture had a compressive strength of 7.3 MPa after 24 hours.

The time of initial setting was measured according to the above Swedish standard SS 137126. Then a value of 6.7±0.5 hours was obtained.

Example 2

The process according to Example 1 was repeated with the difference that a mixture of 3.61 kg/m³ PERAMIN F® (component A) and 0.19 kg/m³ sodium boroheptonate (component C) was produced and added instead of solely PERAMIN F®.

When the mixture of sulphonated melamine-formaldehyde resin and sodium boroheptonate had been admixed to the concrete, the concrete had a slump of 220 mm. At the subsequent measuring of the change of the slump as time goes the following values were obtained. Slump, mm after 20 min 210 after 40 min 190 after 60 min 170 after 80 min 130 after 100 min 120 after 120 min 100 after 140 min 70

Before the additon of the mixture of the compounds A) and C) above, the concrete of course had a slump of 80 mm as in Example 1 since the recipe and the conditions were the same.

In the present case a workability time of about 130 minutes was obtained, which is about 50 minutes longer than according to Example 1. Consequently, an agent according to the invention consisting of a mixture of the components A) and C) gave a considerably longer workability time than a known flowability improving agent consisting of component A).

The difference between the slump value before respectively after the admixture of the flowability improving agent into the concrete also gives a good measure on the flowability improving effect of the agent. In both cases the same difference 140 (220-80) was obtained, which is a good value for a flowability improving agent.

Specimens made of a concrete mixture according to example 2 had a compressive strength of 7.2 MPa after 24 hours, which is directly comparable with the result according to Example 1.

The time of initial setting was measured to 6.9 ± 0.5 hours. Accordingly the difference in time of initial setting between the concrete mixtures of Example 1 and 2 was insignificant and definitively unimportant at the practical use of the invention.

Example 3

The process according to Example 2 was repeated with the difference that solely 0.19 kg/m³ sodium boroheptonate (component C) was used and no sulphonated melamine-formaldehyde resin.

Before the addition of sodium boroheptonate the concrete had a slump of 80 mm and after the addition a slump of 95 mm. This shows that sodium boroheptonate had a insignificant flowability improving effect.

At the subsequent measuring of the change of the slump as time goes the following values were obtained. Slump, mm after 20 min 85 after 40 min 65

Accordingly the sodium boroheptonate gave a workability time of only about 25 minutes.

Test specimens made of the concrete mixture had a compressive strength of 7.5 MPa after 24 hours.

The time of initial setting was measured to 7.1 ± 0.5 hours.

Example 4

The process according to Example 3 was repeated with the difference that solely 3.8 kg/m³ sodium boroheptonate (component C) was used and no sulphonated melamine-formaldehyde resin.

Before the addition of sodium boroheptonate the concrete had a slump of 80 mm and after the addition a slump of 220 mm. Thus, the flowability improving effect became as good as according to Examples 1 and 2.

At the subsequent measuring of the change of the slump as time goes the following values were obtained. Slump, mm after 20 min 215 after 40 min 215 after 60 min 210 after 80 min 200 after 100 min 190 after 120 min 185 after 140 min 170 after 160 min 170

Sodium boroheptonate gave a very long workability time according to the above experiment.

After 7 days test specimens made of the concrete mixture had not been cured yet but had a compressive strength of 0 MPa.

A comparison of the results according to Examples 3 and 4 shows that an insignificant flowability improving effect and workability time was obtained at the use of a rather low content of sodium boroheptonate but that a good compressive strength was obtained after one day.

However, at the use of a higher content of sodium boroheptonate a good flowability improving effect and workability time were obtained. On the other hand the time of initial setting became far too long (several days) and the compressive strength after 7 days was non-existent. Thus, sodium boroheptonate per se did not give the effect which is obtained according to the present invention.

Example 5

The process according to Example 3 was repeated with the difference that solely 0.19 kg/m³ sodium heptonate (accordingly it did not contain any boron) was used and no sulphonated melamine-formaldehyde resin.

Before the addition of sodium heptonate the concrete had a slump of 80 mm and after the addition a slump of 95 mm. This shows that sodium heptonate has an insignificant flowability improving effect.

At the subsequent measuring of the change of the slump as time goes the following values were obtained. Slump, mm after 20 min 80 after 40 min 60

Thus, the sodium heptonate gave a workability time of only 20 minutes.

Test specimens made of the concrete mixture had a compressive strength of 7.7 MPa after one day. The time of initial setting became 7.0 ± 0.5 hours.

Example 6

970 g of a compound A), PERAMIN F® from Perstorp AB and 30 g of a compound D) with the general formula



ArO - [R&sub1;]n - R&sub2;



where Ar is

phenol, R&sub1; is -CH&sub2;CH&sub2;O -, n is 4

and R&sub2; is

were mixed while stirring at a temperature of 35oC until a homogenous mixture was obtained. Then pH was adjusted to 11.0 by addition of sodium hydroxide. The above combination of the components A) and D) in a flowability improving agent is disclosed in the Swedish patent 88.00295-1.

A concrete mixture was produced by mixing for 2 minutes

420 kg/m3 cement (Slite standard Portland)

880 kg/m³ dry gravel 0-8 mm

980 kg/m³ coarse gravel 8-16 mm

206 kg/m³ water

Directly after the production the concrete mixture had a slump of 60 mm measured according to the above method.

Thereafter, 5.5 kg/m³ (1.3 % by weight of the cement) of the mixture of the components A) and D) produced above was admixed for 2 minutes.

Directly after the admixture of the mixture produced of the components A) and D) the concrete mixture had a slump of 220 mm. Then the slump was measured with an interval of 20 minutes. The following values were obtained. Slump, mm after 20 min 180 after 40 min 120 after 60 min 110 after 80 min 80 after 100 min 40

Thus the workability time became about 90 minutes.

Test specimens made of the concrete mixture had a compressive strength of 23.5 MPa after one day.

The time of initial setting of the concrete mixture was measured to 6.7 ± 0.5 hours.

Example 7

The process according to Example 6 was repeated with the difference that 5.3 kg/m³ of the mixture of the compounds A) and D) produced in Example 6 was mixed with 0.2 kg/m³ of the compound C), sodium boroheptonate. The mixture of the compounds A), C) and D) were then admixed to the concrete.

Directly after the admixture of the mixture of the compounds A), C) and D) produced the concrete mixture had a slump of 230 mm. Then the slump was measured with an interval of 20 minutes. The following values were obtained. Slump, mm after 20 min 220 after 40 min 215 after 60 min 200 after 80 min 190 after 100 min 150 after 120 min 130 after 140 min 60

Accordingly the workability time became 140 minutes, since the slump of the concrete before the addition was 60 mm.

Test specimens made of the concrete mixture had a compressive strength of 24.0 MPa after one day.

The time of initial setting of the concrete mixture was measured to 7.0 ± 0.5 hours.

The above results from Examples 6 and 7 shows that a somewhat better flowability improving effect, 230 mm was obtained according to the invention (Example 7) as compared to 220 mm in Example 6. However, above all the workability time was prolonged in Example 7 to a very great extent, 140 min as compared to 90 min in Example 6. The compressive strength after one day as well as the time of initial setting became about the same in the two samples.

Example 8

800 g water and 700 g 37 % formaldehyde were charged into a reaction bulb made of glass. 350 g melamine and 285 g sodiummetabisulphite were added white stirring. The reaction mixture was heated to 75oC while stirring. When the melamine and the sodiummetabisulphite had been completely dissolved and the reaction mixture had cleared up, 18 g 46 % sodium hydroxide was added to get a pH of 10.5 - 11.2. The reaction mixture was kept at 75oC until free sulphite could not be detected any more (0.5 - 2 h).

Then the reaction mixture was cooled down to 50oC. Thereafter 7.0 g of a compound C¹) consisting of boric acid and 18.0 g sulphuric acid (96 %) were added, whereby a pH of 5.8 - 6.1 was obtained. The condensation reaction was then allowed to continue for about 4 hours until a viscosity of 170 cp (Emilia) was obtained. Then the reaction mixture was cooled down to 35o and the pH was adjusted to 11.4 with 25.0 g 46 % sodium hydroxide to give the condensation product a satisfactory storage stability. Thereafter 104 g of a compound C²) consisting of sodium heptonate and 300 g water were admixed for adjusting the solids content to about 35 % by weight.

The process according to Example 2 was repeated with the difference that 3.8 kg/m³ of the mixture of the compounds A), C¹) and C²) produced above was used. When this mixture had been admixed into the concrete the concrete had a slump of 215 mm. At the subsequent measuring of the change of the slump as time goes the following values were obtained. Slump, mm after 20 min 210 after 40 min 200 after 60 min 175 after 80 min 140 after 100 min 110 after 120 min 90 after 140 min 60

As in Example 2 a workability time of about 130 minutes was obtained.

Test specimens made of the concrete mixture had a compressive strength of 7.8 MPa after one day.

The time of initial setting of the concrete mixture was measured to 7.0 ± 0.5 hours.

Example 9

The process according to Example 2 repeated with the difference that 3.61 kg/m³ PERAMIN F® and 0.19 kg/m³ sodium boroheptonate were not mixed with each other. Instead they were added separately to the concrete. The results were the same as in Example 2.


Anspruch[de]
  1. Das Fließfähigkeit-verbesserndes Agens, das auch eine verlängerte Verarbeitbarkeitszeit für eine wäßrige Zement-haltige Zusammensetzung liefert, umfassend eine Kombination aus - auf ein trockenes Produkt bezogen -
    • A) 60 bis 99 Gew.% sulfoniertes Melamin-Formaldehyd-Harz, sulfoniertes Melamin-Harnstoff-Formaldehyd-Harz oder sulfoniertes Naphthalin-Formaldehyd-Harz;
    • C) 0,5 bis 40 Gew.% Bor-haltige Polyhydroxycarbonsäure oder wasserlösliches Alkalisalz oder Erdalkalimetallsalz einer solchen Säure, die per se die folgende Formel hat
      in der R&sub1;
      ist, und

      n 3 bis 8, vorzugsweise 4 bis 6 ist, und möglicherweise
    • D) 0,5 bis 30 Gew.% einer Verbindung der allgemeinen Formel



      Ar O - (R&sub1;)n - R&sub2;



      in der Ar ein möglicherweise substituierter Benzolrest oder Naphthalinrest ist; R&sub1; eine Oxyethylengruppe, -CH&sub2;CH&sub2;-O- oder eine Oxypropylengruppe;
      eine Oxyethylenkette oder eine Oxypropylenkette mit bis zu 15 Oxyethylengruppen oder Oxypropylengruppen oder eine Kombination aus Oxyethylengruppen und Oxypropylengruppen zu einer Kette, in der die Summe dieser Gruppen höchstens 15 ist, darstellt; der durchschnittliche Wert n für n 1 bis 15 ist und R&sub2; Wasserstoff oder eine Phosphonatgruppe der Formel
      in der M&sub1; und M&sub2; Wasserstoffion oder Alkalimetallion sind, ist, oder R&sub2; eine Gruppe der Formel ist:
      in der M&sub2; die oben angegebene Bedeutung hat und M&sub3; -[R&sub1;]n - OAr ist, worin R&sub1;, n und Ar die obengenannten Bedeutungen haben.
  2. Agens nach Anspruch 1, das 70 bis 99 Gew.%, vorzugsweise 80 bis 99 Gew.% Verbindung A); 0,5 bis 30 Gew.%, vorzugsweise 0,5 bis 20 Gew.% Verbindung C) und möglicherweise 0,5 bis 20 Gew.% Verbindung D), bezogen auf ein trockenes Produkt, enthält.
  3. Agens nach Anspruch 1 oder 2, das 70 bis 99 Gew.% Verbindung A), 0,5 bis 20 Gew.% Verbindung C) und 0,5 bis 20 Gew.% Verbindung D, bezogen auf ein trockenes Produkt, enthält.
  4. Agens nach Anspruch 1, das 70 bis 99 Gew.% Verbindung A) und 0,5 bis 30 Gew.% Verbindung C), bezogen auf ein trockenes Produkt, enthält.
  5. Agens nach einem der Ansprüche 1 bis 4, in dem n in der Formel von Verbindung C) 5 ist.
  6. Agens nach einem der Ansprüche 1 bis 5, in dem das Bor in der Verbindung C) als Komplex vorliegt.
  7. Agens nach einem der Ansprüche 1 bis 6, wobei die Verbindung C) aus Zwei Teilkomponenten gebildet worden ist, nämlich aus C¹), Borsäure oder einem wasserlöslichen Salz von Borsäure, und C²) einer Polyhydroxycarbonsäure oder einem wasserlöslichen Alkalisalz oder einem Erdalkalimetallsalz einer solchen Säure, die die-Formel
    hat, in der R&sub1;
    ist; und

    n 3 bis 8, vorzugsweise 4 bis 6 ist.
  8. Verfahren zur Herstellung eines die Fließfähigkeitverbessernden Agenzes, das auch eine verlängerte Verarbeitbarkeit für eine wäßrige Zement-haltige Zusammensetzung liefert, in der eine Verbindung C¹), die aus Borsäure oder einem wasserlöslichen Salz von Borsäure besteht, bei der Herstellung einer Verbindung A), die aus einem sulfonierten Melamin-Formaldehyd-Harz oder einem sulfonierten Melamin-Harnstoff-Formaldehyd-Harz besteht, zugesetzt wird, wobei die vollständige Verbindung A) mit C²) welche aus einer Polyhydroxycarbonsäure oder einem wasserlöslichen Alkalisalz oder einem Erdalkalimetallsalz einer solchen Säure besteht, die die folgende Formel hat
    in der R&sub1;
    ist,

    n 5 bis 8 ist,

    und möglicherweise mit D), einer Verbindung mit der folgenden allgemeinen Formel vermischt wird:



    Ar O -[R&sub1;]n - R&sub2;



    worin A ein möglicherweise substituierter Benzolrest oder Naphthalinrest ist; R&sub1; eine Oxyethylengruppe, -CH&sub2;CH&sub2;-O- oder eine Oxypropylengruppe,
    eine Oxyethylenkette oder eine Oxypropylenkette mit bis zu 15 Oxyethylengruppen oder Oxypropylengruppen oder eine Kombination aus Oxyethylengruppen und Oxypropylengruppen zu einer Kette, in der die Summe dieser Gruppen höchstens 15 ist, darstellt; der durchschnittliche Wert n für n 1 bis 15 ist; und R&sub2; Wasserstoff oder eine Phosphonatgruppe der Formel
    in der M&sub1; und M&sub2; Wasserstoffion oder Alkalimetallion sind;

    oder R&sub2; eine Gruppe mit der Formel ist:
    ist, in der M&sub2; die oben angegebene Bedeutung hat, und M&sub3; -[R&sub1;]n - OAr ist, worin R&sub1;, n und Ar die oben angegebenen Bedeutungen haben.
  9. Verwendung eines die Fließfähigkeit-verbessernden Agenzes auch zur Verlängerung der Verarbeitbarkeitszeit für eine wäßrige Zement-haltige Zusammensetzung, die Beton, Mörtel, Speis und selbstnivellierenden Estrich enthält, wobei das Agens - bezogen auf ein trockenes Produkt -
    • A) 60 bis 99 Gew.% sulfoniertes Melamin-Formaldehyd-Harz, sulfoniertes Melamin-Harnstoff-Formaldehyd-Harz oder sulfoniertes Naphthalin-Formaldehyd-Harz;
    • C) 0,5 bis 40 Gew.% Bor-haltige Polyhydroxycarbonsäure oder wasserlösliches Alkalisalz oder Erdalkalimetallsalz einer solchen Säure, die per se die folgende Formel hat
      in der R&sub1;
      ist, und

      n 3 bis 8, vorzugsweise 4 bis 6 ist, und möglicherweise
    • D) 0,5 bis 30 Gew.% einer Verbindung der allgemeinen Formel



      Ar O - [R&sub1;]n - R&sub2;



      in der Ar ein möglicherweise substituierter Benzolrest oder Naphthalinrest ist; R&sub1; eine Oxyethylengruppe, -CH&sub2;CH&sub2;-O- oder eine Oxypropylengruppe;
      eine Oxyethylenkette oder eine Oxypropylenkette mit bis zu 15 Oxyethylengruppen oder Oxypropylengruppen oder eine Kombination aus Oxyethylengruppen und Oxypropylengruppen zu einer Kette, in der die Summe dieser Gruppen höchstens 15 ist, darstellt; der durchschnittliche Wert n für n 1 bis 15 ist und R&sub2; Wasserstoff oder eine Phosphonatgruppe der Formel
      worin M&sub1; und M&sub2; Waserstofion oder Alkalimetallion sind; oder R&sub2; eine Gruppe mit der Formel:
      ist, in der M&sub2; die obige Bedeutung hat, und M&sub3; -[R&sub1;]n - OAr ist, worin R&sub1;, n und Ar die obige Bedeutung hat.
Anspruch[en]
  1. Flowability improving agent which also gives a prolonged workability time of an aqueous composition containing cement, comprising a combination, calculated on a dry product of
    • A) 60-99 % by weight of a sulphonated melamine-formaldehyde resin, a sulphonated melamine-urea-formaldehyde resin or a sulphonated naphtalene-formaldehyde resin.
    • C) 0.5 - 40 % by weight of a boron containing polyhydroxy carboxylic acid or a water-soluble alkali salt or alkaline earth metal salt of such an acid which per se has got the formula
      where R&sub1; is
      and n is 3-8, preferably 4-6 and possibly
    • D) 0.5 - 30 % by weight of a compound with the general formula



      Ar O - [R&sub1;]n - R&sub2;



      where Ar is a possibly substituted benzene rest or naphtalene rest, R&sub1; is an oxyethylene group;

      - CH&sub2;CH&sub2;O - or an oxypropylene group;
      an oxyethylene chain or an oxypropylene chain with up to fifteen oxyethylene groups or oxypropylene groups or a combination of oxyethylene groups and oxypropylene groups to a chain where the sum of these groups is at most fifteen; the mean value n for n is 1-15 and R&sub2; is hydrogen or a phosphonate group with the formula
      where M&sub1; and M&sub2; are hydrogen ion or alkali metal ion or where R&sub2; is a group with the formula
      where M&sub2; has the above meaning and M&sub3; is - [R&sub1;]n - O Ar

      where R&sub1;, n and Ar have the above meaning.
  2. Agent according to claim 1, containing 70-99 % by weight preferably 80-99 % by weight of compound A), 0.5-30 % by weight preferably 0.5-20 % by weight of compound C) and possibly 0.5 - 20 % by weight of compound D calculated on a dry product.
  3. Agent according to claim 1 or 2, containing 70-99 % by weight of compound A), 0.5 - 20 % by weight of compound C) and 0.5 - 20 % by weight of compound D calculated on a dry product.
  4. Agent according to claim 1, containing 70-99 % by weight of compound A) and 0.5 - 30 % by weight of compound C) calculated on a dry product.
  5. Agent according to any one of claims 1-4, wherein n in the formula of compound C) is 5.
  6. Agent according to any one of claims 1-5, wherein the boron is present as a complex in the compound C).
  7. Agent according to any one of claims 1-6, wherein the compound C) has been formed by two partial components namely C¹), boric acid or a water-soluble salt of boric acid and C²) a polyhydroxy carboxylic acid or a water-soluble alkali salt or an alkaline earth metal salt of such an acid having the formula
    where R&sub1; is
    and n is 3-8, preferably 4-6.
  8. Process for the production of a flowability improving agent which also gives a prolonged workability time of an aqueous composition containing cement wherein a compound C¹) consisting of boric acid or a water-soluble salt of boric acid is added at the production of a compound A) consisting of a sulphonated melamine-formaldehyde resin or a sulphonated melamine-urea-formaldehyde resin, that the complete compound A) is mixed with C²) consisting of a polyhydroxy carboxylic acid or a water soluble alkali salt or an alkaline earth metal salt of such an acid having the formula
    where R&sub1; is
    and n is 5-8 and possibly D), a compound with the general formula.



    Ar O - [R&sub1;]n - R&sub2;



    where Ar is a possibly substituted benzene rest or naphtalene rest, R&sub1; is an oxyethylene group;

    - CH&sub2;CH&sub2;O - or an oxypropylene group;
    an oxyethylene chain or an oxypropylene chain with up to fifteen oxyethylene groups or oxypropylene groups or a combination of oxyethylene groups and oxypropylene groups to a chain where the sum of these groups is at most fifteen; the mean value n for n is 1-15 and R&sub2; is hydrogen or a phosphonate group with the formula
    where M&sub1; and M&sub2; are hydrogen ion or alkali metal ion or where R&sub2; is a group with the formula
    where M&sub2; has the above meaning and M&sub3; is - [R&sub1;]n - O Ar

    where R&sub1;, n and Ar have the above meaning.
  9. Use of a flowability improving agent also for prolonging the workability time of an aqueous cement containing composition comprising concrete, grouts, mortars, and self levelling floor screeds, which agent calculated on a dry product comprises.
    • A) 60-90 % by weight of a sulphonated melamine-formaldehyde resin, a sulphonated melamine-urea-formaldehyde resin or a sulphonated naphtalene-formaldehyde resin.
    • C) 0.5 - 40 % by weight of a boron containing polyhydroxy carboxylic acid or a water-soluble alkali salt or alkaline earth metal salt of such an acid which per se has got the formula
      where R&sub1; is
      and n is 3-8, preferably 4-6 and possibly
    • D) 0.5 - 30 % by weight of a compound with the general formula



      Ar O - [R&sub1;]n - R&sub2;



      where Ar is a possibly substituted benzene rest or naphtalene rest, R&sub1; is an oxyethylene group;

      - CH&sub2;CH&sub2;O - or an oxypropylene group;
      an oxyethylene chain or an oxypropylene chain with up to fifteen oxyethylene groups or oxypropylene groups or a combination of oxyethylene groups and oxypropylene groups to a chain where the sum of these groups is at most fifteen; the mean value n for n is 1-15 and R&sub2; is hydrogen or a phosphonate group with the formula
      where M&sub1; and M&sub2; are hydrogen ion or alkali metal ion or where R&sub2; is group with the formula
      where M&sub2; has the above meaning and M&sub3; is - [R&sub1;]n - O Ar

      where R&sub1;, n and Ar have the above meaning.
Anspruch[fr]
  1. Agent améliorant la fluidité qui prolonge aussi le temps d'aptitude à la mise en oeuvre d'une composition aqueuse contenant un ciment, lequel agent dont les proportions sont calculées par rapport au produit sec, est constitué d'une composition de
    • A) 60 à 99 % en poids de résine formaldéhyde-mélamine sulfonée, de résine formaldéhyde-urée-mélamine sulfonée ou de résine formaldéhyde-naphtalène sulfonée
    • C) 0,5 à 40 % en poids d'un acide carboxylique polyhydroxylé contenant du bore ou d'un sel alcalin soluble dans l'eau ou d'un sel de métal alcalino-terreux d'un tel acide qui répond en soi à la formule
      dans laquelle R&sub1; représente
      et n vaut 3 à 8, de préférence 4 à 6 et éventuellement
    • D) 0,5 à 30 % en poids d'un composé répondant à la formule générale



      Ar O - [R&sub1;]n - R&sub2;



      dans laquelle Ar représente un résidu benzène ou naphtalène éventuellement porteur d'un substituant, R&sub1; représente un groupe oxyéthylène -CH&sub2;CH&sub2;O- ou un groupe oxypropylène
      une chaîne oxyéthylène ou oxypropylène ayantjusqu'à quinze groupes oxyéthylène ou oxypropylène ou une combinaison des groupes oxyéthylène et oxypropylène dans une chaîne où la somme de ces groupes est au plus de quinze; n possède une valeur moyenne n comprise entre 1 et 15 et R&sub2; représente un atome d'hydrogène ou un groupe phosphonate de formule
      dans laquelle M&sub1; et M&sub2; représentent union de type hydrogène ou un ion de type métal alcalin ou dans laquelle R&sub2; représente un groupe répondant à la formule
      dans laquelle M&sub2; a la même signification que ci-dessus et M&sub3; représente -[R&sub1;]n-OAr dans laquelle R&sub1;, n et Ar ont la même signification que ci-dessus.
  2. Agent conforme à la revendication 1, contenant 70 à 99 % en poids et de préférence 80 à 99% en poids de composé A), 0,5 à 30 % en poids et de préférence 0,5 à 20% enpoids de composé C) et éventuellement 0,5 à 20 % en poids de composé D), proportions calculées par rapport au produit sec.
  3. Agent conforme à la revendication 1 ou 2, contenant 70 à 99 % en poids de composé A), 0,5 à 20 % en poids de composé C) et 0,5 à 20 % en poids de composé D), proportions calculées par rapport au produit sec.
  4. Agent conforme à la revendication 1, contenant 70 à 99 % en poids de composé A) et 0,5 à 30% de composé C), proportions calculées parrapport au produit sec.
  5. Agent conforme à une quelconque des revendications 1 à 4, dans lequel l'indice n dans la formule du composé C) vaut 5.
  6. Agent conforme à une quelconque des revendications 1 à 5, dans lequel le bore est présent sous forme d'un complexe dans le composé C).
  7. Agent conforme à une quelconque des revendications 1 à 6, dans lequel le composé C) est constitué de deux composants partiels à savoir C¹) qui est de l'acide borique ou un sel soluble dans l'eau de l'acide borique et C²) qui est de l'acide carboxylique polyhydroxylé ou un sel alcalin soluble dans l'eau ou un sel de métal alcalino-terreux d'un tel acide répondant à la formule
    dans laquelle R&sub1; représente
    et n vaut 3 à 8, de préférence 4 à 6.
  8. Procédé pour la production d'un agent améliorant la fluidité qui prolonge aussi le temps d'aptitude à la mise en oeuvre d'une composition aqueuse contenant un ciment dans lequel un composé C¹) qui consiste en un acide borique ou un sel soluble dans l'eau de l'acide borique est ajouté à la fabrication d'un composé A) constitué d'une résine formaldéhyde-mélamine sulfonée ou d'une résine formaldéhyde-urée-mélamine sulfonée, lequel composé A) complet est mélangé avec C²) constitué d'un acide carboxylique polyhydroxylé ou d'un sel alcalin soluble dans l'eau ou d'un sel de métal alcalino-terreux d'un tel acide répondant à la formule
    dans laquelle R&sub1; représente
    et n vaut 5 à 8 et éventuellement D), composé répondant à la formule générale



    Ar O - [R&sub1;]n - R&sub2;



    dans laquelle Ar représente un résidu benzène ou naphtalène éventuellement porteur d'un substituant, R&sub1; représente un groupe oxyéthylène; -CH&sub2;CH&sub2;O- ou un groupe oxypropylène;
    une chaîne oxyéthylène ou oxypropylène ayant jusqu'à quinze groupes oxyéthylène ou oxypropylène ou une combinaison des groupes oxyéthylène et oxypropylène dans une chaîne où la somme de ces groupes est au plus de quinze; n possède une valeur moyenne n comprise entre 1 et 15 et R&sub2; représente un atome d'hydrogène ou un groupe phosphonate de formule
    dans laquelle M&sub1; et M&sub2; représentent un ion de type hydrogène ou un ion de type métal alcalin ou dans laquelle M&sub2; représente un groupe répondant à la formule
    dans laquelle M&sub2; a la même signification que ci-dessus et M&sub3; représente -[R&sub1;]n-OAr dans laquelle R&sub1;, n et Ar ont la même signification que ci-dessus.
  9. Utilisation d'un agent améliorant la fluidité et prolongeant aussi le temps d'aptitude à la mise en oeuvre d'une composition aqueuse de ciment comprenant le béton, les enduits, les mortiers et des matériaux de ragréage auto-nivelant du sol, lequel agent dont les proportions sont calculées par rapport au produit sec, comprend
    • A) 60 à 90 % en poids d'une résine formaldéhyde-mélamine sulfonée, d'une résine formaldéhyde-urée-mélamine sulfonée ou d'une résine formaldéhyde-naphtalène sulfonée.
    • C) 0,5 à 40 % en poids d'un acide carboxylique polyhydroxylé ou d'un sel alcalin soluble dans l'eau ou d'un sel de métal alcalino-terreux d'un tel acide qui répond en soi à la formule
      dans laquelle R&sub1; représente
      et n vaut 3 à 8, de préférence 4 à 6 et éventuellement
    • D) 0,5 à 30 % en poids d'un composé répondant à la formule générale



      Ar O - [R&sub1;]n - R&sub2;



      dans laquelle Ar représente un résidu benzène ou naphtalène éventuellement porteur d'un substituant, R&sub1; représente un groupe oxyéthylène; -CH&sub2;CH&sub2;O- ou un groupe oxypropylène;
      une chaîne oxyéthylène ou oxypropylène ayant jusqu'à quinze groupes oxyéthylène ou oxypropylène ou une combinaison des groupes oxyéthylène et oxypropylène dans une chaîne où la somme de ces groupes est au plus de quinze; n possède une valeur moyenne n comprise entre 1 et 15 et R&sub2; représente un atome d'hydrogène ou un groupe phosphonate de formule
      dans laquelle M&sub1; et M&sub2; représentent un ion de type hydrogène ou un ion de type métal alcalin ou dans laquelle M&sub2; représente un groupe répondant à la formule
      dans laquelle M&sub2; a la même signification que ci-dessus et M&sub3; représente -[R&sub1;]n-OAr dans laquelle R1, n et Ar ont la même signification que ci-dessus.






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