EP1608710A2

EP1608710A2 - Associative thickener preparation

Info

Publication number: EP1608710A2
Application number: EP04718214A
Authority: EP
Inventors: Helmut Coutelle; Klaus Dziwok
Original assignee: Sued Chemie AG
Current assignee: Rockwood Clay Additives GmbH
Priority date: 2003-03-08
Filing date: 2004-03-07
Publication date: 2005-12-28
Also published as: CN1777657A; WO2004078858A3; CN100540617C; JP2006520414A; DE10310175A1; WO2004078858A2; US20070161745A1

Abstract

An associative thickener preparation is disclosed with a viscosity in aqueous solution of less than 25,000 mPas, comprising (a) a combination of at least one pseudoplastic associative thickener (A) and at least one newtonian associative thickener (B) and/or (b) a combination of at least one pseudoplastic associative thickener (A), at least one newtonian associative thickener (B) and at least one thinner (C) and/or (c) a combination of at least one pseudoplastic associative thickener (A), at least one newtonian associative thickener (B) and at least one wetting agent and/or (d) a combination of at least one pseudoplastic associative thickener (A), at least one newtonian associative thickener (B) and at least one solvent and/or (e) a combination of at least one pseudoplastic associative thickener (A), at least one newtonian associative thickener (B), at least one solvent and at least one wetting agent and/or (f) a combination of at least one pseudoplastic associative thickener (A) and at least one thinner (C) and/or (g) a combination of at least one newtonian thickener (B) and at least one thinner (C).

Description

PATENT APPLICATION

Assoziatiwerdickerpräparation

description

Associative thickeners have been known thickeners for aqueous systems for many years. They come u. a. used in dispersion-based aqueous paints and varnishes, but also other aqueous systems, e.g. Cleaning agents, cosmetics, stripping agents, aqueous pigment pastes, car paints, industrial paints, printing inks, lubricating greases, plaster and wall paints, textile coatings, pharmaceutical preparations, crop protection formulations, filler dispersions, adhesives, detergents, wax dispersions, polishes, aids for tertiary oil production etc. rheologically adjusted.

The typical mode of action of these thickeners is due to their chemical structure. In general, associative thickeners consist of a water-soluble hydrophilic main part, ie a water-soluble polymer chain, which mostly consists of polyethylene glycol or also of cellulose derivatives, acrylate chains, polyether chains or polyester chains, hydrophobic groups being attached to these polymer chains. Both parts are bound to each other by the most diverse types of covalent bonds. The linkage can be brought about, for example, by urethane bonds, ester bonds, ether bonds, urea bonds, carbonate bonds or amide bonds.

The usual production of the associative thickener takes place by the fact that e.g. bifunctional alcohols (usually polyethylene glycol) react with bifunctional reactants (usually diisocyanates) in a polyaddition reaction and the addition reaction is ended by adding monofunctional reactants (e.g. monofunctional alcohols such as nonylphenol ethoxylate). The hydrophobic groups required for the formation of the associative interaction are then bound to the water-soluble polymer chains.

The hydrophilic part remains dissolved in the application system in the aqueous phase. However, the hydrophobic groups attach themselves to hydrophobic surfaces, for example to the dispersed or emulsified organic binders in an aqueous coating, for example an emulsion paint, to the hydrophobic surfaces of fillers, pigments etc. Since a thickener polymer normally has two terminal ends (or several additional) hydrophobic parts, it can attach to several dispersion particles at the same time. These are linked together using the hydrophilic base chain. This creates a thickening effect, which is based on the association of the hydrophobic or the less water-soluble components and the construction of a three-dimensional one Network by means of van der Waals' interactions in the aqueous system. Hence the name associative thicker.

It is in the nature of this mechanism that the hydrophobic components but not only with the hydrophobic components e.g. in one color, associate. The hydrophobic groups also associate with one another in the absence of a dispersion or other hydrophobic constituents and form e.g. Micelles. This also leads to a thickening. This thickening also takes place when only the thickening polymer alone is dissolved in water. Since the usual form of delivery of the polymer is an aqueous solution, it is understandable that excessive thickening is not desirable here. This makes processing or handling more difficult or limits the maximum concentration of the soluble thickener polymer in water to small percentages.

The rheological effects of the thickener can be adjusted by selecting the hydrophobic end groups and / or adjusting the molecular weight, so that Newtonian associative thickeners (B) or also relatively pronounced structurally viscous associative thickeners (A) are produced. In the latter case, the thickening in water alone is particularly pronounced due to the intermolecular interaction and the need is particularly great to lower the viscosity so that acceptable polymer concentrations can also be offered here in a manageable form.

In order to suppress the high viscosity of the structurally viscous associative thickener (A) in water alone and thus to make the thickener easier to handle or to be able to offer in higher concentration, a whole range of possibilities have already been developed, which have been implemented and used for years become. The usual way to reduce the viscosity is to add solvents. For this purpose, especially glycols, such as propylene glycol, butyl glycol, butyl diglycol and butyl triglycol, are used. However, these products are typical solvents that can be released into the environment. For this reason, these are no longer desirable in newer color formulations, for example for ecological reasons. The thinning effect is essentially due to the fact that these solvents themselves have a typical surfactant-like structure with a readily water-soluble end (alcohol / glycol) and a water-insoluble fraction (butyl group, etc.). The polarity by addition of the hydrophobic alkyl group to the hydrophobic group of the Assoziatiwerdickermoleküls "reversed" and the intensive interaction of the thickener molecules suppressed to each other or reduced. _This. .Is to recognize in some cases also to the phenomenon that such liquid set Verdickerlδsungen on addition of water first become thicker because the water-soluble solvents are diluted and their effect is reduced.

As part of the development of VOC-free (VOC = volatile organic content) or emission-free paints and varnishes, the manufacturers were given the desire for associative thickeners that are free of these solvents. EP-A-0 614 950 describes one way of achieving this. Cyclodextrin is used here to suppress the solution viscosity of strongly structurally viscous associative thickeners in the delivery form without using solvents. The hydrophobic parts of the thickener are adsorbed in the hydrophobic parts of the cyclodexrin and prevented from mutual interactions. The disadvantage is that the cyclodextrins remain in the system, for example in color, after the associative thickener has been released. This now released adsorption sites in the cyclodextrin can thus adsorb other formulation components, such as wetting and dispersing agents, and thus render them ineffective. In addition to other problems, this can also lead to stability problems in the systems, such as a color. This means that the amount of these necessary additives has to be optimized and the formulation adapted to the thickener, which is not desirable.

Another way has also been used for years. The property of real non-ionic surfactants or emulsifiers (compared to butyl diglycol and other higher molecular materials) is used to reduce the viscosity of associative thickeners. These are not released into the environment through "evaporation", since their boiling point is too high, and thus remain largely in the paint, for example, after a paint has dried. However, they then have the disadvantage of reducing the water resistance, for example of these paints, because they make the ink film as water-soluble and thus also water-attracting constituents more easily swellable and removable, and their use can lead to foam problems in the production of ink.

For this reason, in addition to the (reduced) solvent content and a surfactant, the further addition of a "defoamer" ("Surfynol") is described in EP-B-0 682 094.

Further prior art in these areas are e.g. WO 00/00539, DE-A-196 44 933, DE-A-43 10 702, DE-A-195 23 837, DE-A-196 00 467, US-A-4, 079, 028 and DE -A-14 44 243.

In US-A-2002/0052441 sodium formate is described as an additive. However, salts cause considerable water resistance problems in industrial paints and also decorative paints. The use of polypropylene or polybutylene glycols in thickeners is described in numerous patent applications or the possibility is mentioned, for example in EP-A-0 031 777. The purpose of the polypropylene glycol portion here is only to reduce the melting point. According to WO-A-01/85821, the addition of polybutylene glycol means that the thickener is soluble in solvents, not in water. According to EP-B-0 642 557, no sense or advantage of a possible proportion of a polypropylene glycol in the thickener is defined. In none of the cases mentioned was a viscosity-reducing effect on the aqueous solution viscosity of the thickener polymers by the replacement or partial replacement of polyethylene glycol by propylene or butylene glycol described.

DE-A-36 30 319 describes polyurethane thickeners based on polypropylene / polyethylene glycol copolymers. Here, the intended thickeners themselves should be liquids, not solids, which should therefore be pourable directly in water without a previous solution and therefore should not be dissolved in water as the delivery form, but should be approximately 100% liquid as an active ingredient. It is also mentioned here that the thickening profile in the application system can be varied by combining several thickeners. However, the influence of the mixture of thickeners or the influence of propylene glycol-polyethylene glycol copolymer components in the thickener on the reduction of the solution viscosity of the thickener polymers in water was not mentioned or recognized. However, it is generally known that 100% associative thickeners, whether liquid or in powder form, are difficult to incorporate into aqueous systems since they have a strong tendency to form lumps. For this reason alone, thickeners are predominantly used in water that can be used easily and easily. xibel can be added to the aqueous system if the viscosity is low enough so that the system is pourable.

However, all of these proposals have the disadvantage that the additives suppress or reduce the viscosity development in water as desired, but these additives are undesirable for ecological reasons (solvent / co-solvent) or usually have negative side effects in the resulting coating film.

The object of the present invention was therefore to provide an associative thickener which can be dissolved in water in as high a concentration as possible without having too high a viscosity due to intermolecular association. Furthermore, the viscosity should be reduced without the use of solvents or condensers that can get into the atmosphere according to the VOC guideline (ie substances with a boiling point <250 ° C) or emit emissions, e.g. ammonia or formaldehyde, into the environment , According to the RAL-ZU 102 (basis for environmental label of May 2000, page 3) are to be understood as VOC all organic substances which by total evaporation and subsequent gas chromatographic analysis to Retentionszei ^'of the substance tetradecane t (boiling point: 252, 6 ° C) elute on a non-polar column.

Finally, a way to suppress viscosity should be found using only rheologically active ingredients.

Surprisingly, it was found that the viscosity of an associative thickener preparation in aqueous solution was less can be reduced to 25,000 mPas if the associative thickener preparation contains:

(a) a combination of at least one pseudoplastic associative thickener (A) and at least one Newtonian associative thickener (B); and or

(b) a combination of at least one pseudoplastic associative thickener (A), at least one Newtonian associative thickener (B) and at least one plasticizer (C); and or

(c) a combination of at least one pseudoplastic associative thickener (A), at least one Newtonian associative thickener (B) and at least one wetting agent; and or

(d) a combination of at least one pseudoplastic associative thickener (A), at least one Newtonian associative thickener (B) and at least one solvent; and or

(e) a combination of at least one structurally viscous associative thickener (A), at least one Newtonian associative thickener (B), at least one solvent and at least one wetting agent; and or

(f) a combination of at least one pseudoplastic thickener (A) and at least one plasticizer (C); and or

(g) a combination of at least one Newtonian thickener (B) and at least one condenser (C). Since the transition from Newtonian (B) to structurally viscous (A) associative thickener is fluid, the following definition applies according to the invention:

An associative thickener is said to be Newtonian (B) if its solution viscosity in 20% aqueous solution is less than 20,000 mPas (Brookfield viscometer, 20 rpm).

In order to really be called an associative thickener and to ensure a clear differentiation from low molecular weight surfactants, this should at the same time cause a thickening in an emulsion system. To determine this, 2.5 parts of the thickener are mixed into a mixture of 100 parts by weight of Acronal 290D (BASF, aqueous styrene-acrylate dispersion), 30 parts by weight of deionized water and 0.3 part by weight of defoamer ADDID 800 (Wacker, silicone defoamer for aqueous dispersions) stirred in homogeneously. The viscosity at 10,000 sec ^"1 (Bohlin viscometer) after 4 hours of ripening is at least 50% higher than that of the blank sample. At the same time, the molecular weight should be above 2500 g / mol, in particular above 1000 g / mol.

An associative thickener is referred to here as shear thinning (A) if its solution viscosity in 20% aqueous solution is more than 100,000 mPas and the viscosity in the Acronal Test System at a shear rate of 1 sec ^{"1 is} more than 10,000 mPas (zu In this measurement, the structurally viscous associative thickener is mixed with 16% by weight butyl diglycol as a viscosity-reducing substance in order to be processable: 20% by weight thickener + 16% by weight butyl diglycol + 64% by weight water). The combination according to the invention of structurally viscous associative thickener (A) and Newtonian thickener (B) or / and plasticizer must have a low shear thickening at 1 sec ^"1 of at least 10,000 mPas in the acronal system ^" as a structurally viscous and 2.5 g of the thickener are homogeneously stirred into a mixture of 100 g of Acronal 290D (BASF), 30 g of deionized water and 0.3 g of defoamer ADDID 800 (Wacker) and measured after a rest period of 4 hours.

Preferred embodiments of the invention are specified in the subclaims.

The invention further relates to a method for producing the above-defined association of thickener preparation, which is characterized in that

a) ■ at least one structurally viscous associative thickener

(A) dissolves in water together with at least one Newtonian associative thickener (B);

b) at least one structurally viscous associative thickener

(A) dissolves in water together with at least one Newtonian associative thickener (B) and at least one plasticizer (C);

c) at least one structurally viscous associative thickener

(A) dissolves in water and adds at least one plasticizer (C);

d) at least one structurally viscous associative thickener (A) and one Newtonian associative thickener (B) for further teren lowering the viscosity together with a solvent and / or surfactant in water, using a dispersing and / or wetting agent as the surfactant and a glycol with a boiling point> 250 ° C as the solvent.

The invention furthermore relates to the use of the above-defined association of thickener preparation for adjusting the rheology of dispersion-bound aqueous paints and varnishes or other aqueous systems from the group of cleaning agents, cosmetics, stripping agents, aqueous pigment pastes, car paints, industrial paints, printing inks, greases, cleaning agents and Wall paints, textile coatings, pharmaceutical preparations, crop protection formulations, filler dispersions, adhesives, detergents, wax dispersions, polishes and auxiliaries for tertiary oil production.

It was surprisingly found that the addition of a Newtonian associative. Thickener (B), which is soluble in water alone, to a structurally viscous thickener (A) dissolved in water alone, does not cause the expected additional strong viscosity increase in the aqueous delivery form, as would have been calculated if the individual viscosities of separate solutions had been added , Depending on the choice of the proportions and the type of both thickeners, it is even possible to reduce the viscosity of the pseudoplastic thickener, dissolved in water alone, although the total polymer content of the aqueous solution is significantly increased. It is not necessary to add solvents in order not to exceed a maximum viscosity of 25,000 mPas.

Aqueous solutions of a structurally viscous associative thickener (A) without the addition of solvents or plasticizers were prepared. provides. The concentration was gradually reduced from 20% by weight. A concentration was determined at which the solution viscosity was lower than 25,000 mPas. The amount of undissolved 100% Newtonian associative thickener (B) missing to 20% was now added to this solution. In the cases mentioned in the examples, the solution viscosity was in no way increased in the same ratio as Newtonian thickener was added. In most cases, the viscosity remained alone at or below the value of the viscosity of the pseudoplastic thickener, even though the total polymer content of associative thickeners was increased up to 5 times. Usually, the viscosity increases when thickeners are added to the individual thickener in the nonlinear additive range, in the relevant viscosity range of 2,000 to 25,000 mPas, almost exponentially.

Despite the fact that the solution viscosity is not increased, the addition of the Newtonian thickener (B) in the application system results in a significantly stronger thickening. Extreme increases have been recorded, particularly in the high shear area.

The addition of a Newtonian thickener (B) to a structurally viscous associative thickener leads to an increased thickening effect in the application system. In contrast, in the aqueous solution, the addition of the Newtonian thickener (B) only results in a subadditive increase in the solution viscosity or even a reduced viscosity compared to that of the pseudoplastic thickener portion alone.

Depending on the chemical composition of the pseudoplastic associative thickener (A), it may be a special one Newtonian associative thickener (B) necessary to reduce the viscosity particularly well.

The viscosity of an aqueous solution of e.g. pseudoplastic thickener (A) in water can also be suppressed by special plasticizers (C), e.g. by the copolymers described in more detail below. The alternating hydrophilic / hydrophobic co-poly can be produced by the co-condensation or co-polymerization of hydrophilic molecules or oligomers (D) with hydrophobic molecules (E).

The hydrophilic molecules or oligomers (D) can be selected from Z- [CH ₂ CH2-0] _m -CH ₂ CH ₂ -Z2, where m = 0 to 15, preferably m = 2 to 6, and Z and Z ₂ , which are identical or different from one another, represent an active hydrogen-containing group, such as OH, NH ₂ or secondary amines. Short-chain polyethylene glycols are preferably used.

The hydrophobic portions (E) can be selected from XRX ₂ , where R is a saturated or unsaturated aliphatic or cycloaliphatic radical having 2 to 12 carbon atoms, preferably having 3 to 6 carbon atoms, or an aromatic radical having 6 to 12 carbon atoms. Atoms, or a mixed aromatic / aliphatic radical having 6 to 17 carbon atoms and X and X ₂ , which are the same or different and mean a function which can be reacted with Z and Z ₂ , for example a carboxylic acid, carboxylic anhydride, carboxylic acid chloride , Ester, isocyanate, epoxy group or a halogen ion. Adipic acid, phthalic anhydride or dimethyl terephthalate are preferably used. The ratio of D / E is approximately 6: 5 to 5: 6, preferably approximately 3: 2 to 2: 3, in particular approximately 2: 1 to 1: 2. This means that these materials also differ significantly from the usual materials used as plasticizers in accordance with VdL-RL 01 (Guideline for the Declaration of Ingredients in Architectural Coatings, Architectural Paints and Related Products, revised edition from April 2000), for example di-n-octyl phthalate , Di-n-butyl phthalate etc. are listed. In contrast to the plasticizers mentioned above, these materials do not contain any hydrophilic components.

In Farb & Lack, 7/2002, Gerald Altnau, p.37ff, dibasic esters of adipic acid are proposed as film-forming aids or VOC-free solvents because of their high boiling point and low vapor pressure. Copolymers of diacids with polyethylene glycols are not mentioned. The use as a plasticizer (C) in associative thickener preparations accordingly also saves the addition of film auxiliaries or reduces their use.

Optionally, one or two terminating end groups with only one reactive function Z, Z ₂ , X, or X _{2 can be} included.

If short-chain ethylene glycols are used in a small molar excess, the desired property is also obtained that the oligomer or polymer itself is poorly soluble in water and partly shows phase separation with water, but still has vicosity-reducing properties in the test system and is homogeneously distributed without phase separation. In the application system, this leads to an improvement in the water resistance after the paint has dried. If the acid is used in excess and then neutralized in aqueous NaOH, after evaporation of the water with acid numbers from about 80 mg KOH / g Copolymers of ethylene glycol and propylene glycol and / or butylene glycol can also be used as alternating hydrophilic / hydrophobic copolymers. The statistical copolymers are preferred here over the block copolymers. The copolymer can be added to the thickener as a pure condenser or can be covalently incorporated into the thickener. Polypropylene glycol components or polypropylene / polyethylene glycol copolymers, incorporated in the thickener polymer, reduce the solution viscosity of the thickener in water. The pure admixture of polypropylene glycol / polyethylene glycol copolymers also lowers the aqueous solution viscosity of the thickener. The molar proportion of propylene glycol and / or butylene glycol in the polyethylene glycol is ideally between 10 and 60 mol%. Pure polypropylene glycols are too poorly water-soluble and show less condensing action, as are pure polybutylene glycols. However, relatively short chain propylene or butylene glycols can be used, are water soluble and have a plasticizing effect. These are preferably oligomeric propylene or butylene glycols with up to 10 monomer units. The propylene glycols preferably have a molecular weight of up to about 700 g / mol, the butylene glycols of up to about 500 g / mol. Block copolymers such as PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol) are usually less effective. Polyethylene glycol polymers are readily soluble, but their effect is insufficient.

Hexanediol can also be used. This has a boiling point of over 253 ° C and is therefore not a VOC; it also has the additional advantage that it is solid at room temperature and therefore does not increase the stickiness and dirt absorption of the paint film.

The following examples are intended to explain the present invention in more detail without restricting the possibilities of the methodology. To clarify the effectiveness, the following created the examples. For reasons of comparison, a solids content of 20% by weight of the water-soluble polymer in water was predominantly used. In addition to the amount of 20% by weight of an associative thickener or a corresponding mixture of associative thickeners (A + B), plasticizers or - in comparison - standard solvents were also used.

As structurally viscous thickeners (A), hydrophobically modified, ethoxylated aminoplasts, i.e. the pure 100% solid polymers (without water and butyl diglycol) of the following commercial products from Süd-Chemie AG are used. The solid polymers can be obtained from the commercial products by evaporating off the solvents; however, the polymers can also be used directly after preparation, before they are dissolved:

H375 (solid polymer from commercial product Optiflo H370) * H405 (solid polymer from commercial product Optiflo H400) * H605 (solid polymer from commercial product Optiflo H600) *

* Solution viscosity in water cf. Table I and II

Hydrophobically modified ethoxylated aminoplasts, i.e. the pure solid polymers (without water) of the following commercial products from Süd-Chemie AG are used:

L105 (solid polymer from commercial product Optiflo L100) * L155 (solid polymer from commercial product Optiflo L150) **

* Solution viscosity in water cf. Table II ** Solution viscosity 20% by weight in water 10,000 to 12,000 mPas

The degree of hydrophobicity is higher in the case of the H types than in the case of the L types.

In order to clarify that this invention is not only limited to the solids content of existing commercial products and has general validity, the further simple ones mentioned in the examples were made according to the production processes described in WO 96/40815, WO 96/40625 and WO 96/40626 Model thickener manufactured and tested.

The raw materials were used in a molar ratio. The individual amount used was calculated on the total amount used in the patent applications indicated. The catalysts were used in the same proportions as specified in the patent applications.

Examples 1 to 10 (comparison)

Example 1 shows the viscosity of the test binder, Acronal 290 D from BASF (styrene acrylate dispersion). Examples 2 to 10 show both the viscosities of the various aqueous solutions of a pseudoplastic thickener (H375) and extracts the thickening effect of these associative thickener solutions in Acronal 290 D. The results are shown in Table I. Table I

Comparative values of the pseudoplastic H375 thickener

Examples 11 to 15 (according to the invention) and Examples 16 and 17 (comparison)

The results are shown in Table II.

As Examples 11 to 15 show, the viscosity of the thickener mixtures in water is below the expected additive viscosity of the individual components; this is not the case in the Tes binder. There the viscosity largely corresponds to the additive viscosity or there is an even greater thickening. Table II

Mixtures of pseudoplastic and Newtonian thickeners pseudoplastic H375 Newtonian L105

Examples 18, 20, 22, 24, 25, 27, 29, 31, 33, 35, 40, 44 to 46,

49, 50 (according to the invention) and 19, 21, 23, 26, 28, 30, 32, 34, 36,

37 to 39, 41 to 43, 47, 48 (comparison)

The values in Table III show the reduction in viscosity of aqueous solutions of pseudoplastic thickeners (here H 375, H405, H605 or VI) by adding Newtonian thickeners (here L 105, L 155, V4, V5, V6, V8, V9, V10, _VI1. V12) in comparison to the liquefaction effect of Standardlδsemittels butyldiglycol (BDG). As can be seen, the thickening effect of the preparations according to the invention in the test binder is similar to that of the pure addition of the individual contributions of the thickeners A + B (example 24 or 27), although the solution viscosity in water is lower than expected when combining A + B would. As examples 47 to 50 show, it is entirely possible to produce a Newtonian thickener for a pseudoplastic thickener (VI) by modifying the composition, which has a particularly good dilution effect (V4 compared to the L 155).

Table III

Mixtures of pseudoplastic and Newtonian thickeners pseudoplastic H375, H405, H605, VI Newtonian L105, L155, V2 to V13

Examples 51 to 59

Table IV shows the influence of various new plasticizers (C) on the solution viscosity of the pseudoplastic thickeners H375 and H605.

The liquefiers (C) were produced as follows:

Method 1 (starting from the ester):

101 g of tetraethylene glycol (0.5 mol) are dried for 2 hours at 100 ° C and 20 hPa. Then 90 g of dimethyl adipate (0.5 mol) and then 1 g of 30% methanolic solution of NaOMe are added. The methanol formed is removed in vacuo at 100 ° C. with stirring until the bubbles have stopped. Then the vacuum is broken and 0.3 g of glacial acetic acid (equimolecular to the NaOMe used) is stirred in.

Method 2 (starting from the acid):

Instead of the X, X ₂ = ester on the hydrophobic part (E), the X, X ₂ = acid is used. The reaction is carried out under toluenesulphonic acid catalysis at about 120-220 ° C under vacuum and ended as soon as most of the theoretically calculated water has been removed in vacuo and is deposited in the cold trap. Xylene may be used as a tractor for traces of residual water, and the xylene / water mixture is collected in a water separator.

The products are slightly viscous up. viscous / solid.

As shown in Table IV, the liquefaction effect of the liquefiers C1 to C9 (Examples 51 to 59) was tested. Just- if commercially available copolymers (CIO to C15) were tested as plasticizers (Examples 60 to 66). The esters (Cl to C9) show a pronounced liquefaction effect. The CIO copolymer is also effective as a plasticizer. The thickening effect in the test binder is very pronounced and roughly equivalent to the preparation made with the standard plasticizer BDG, sometimes even higher (Examples 53, 57 and 61) than the comparison with the standard plasticizer BDG (Example 3). The homo- or block copolymers C1 to C15 are far less effective as plasticizers than the statistical hydrophilic-hydrophobic copolymer CIO.

Table IVa

Adding a plasticizer C1 to C9 hydrophobic / hydrophilic copolymers as admixtures to the pseudoplastic thickener

Table IVb

Add a plasticizer CIO statistical PPG / PEG (1: 1) polyglycol as an admixture to the pseudoplastic thickener

Example 67 (according to the invention) and 68 to 71 (comparison)

Table V shows an example of the use of a statistical hydrophilic-hydrophobic copolymer as part of the associative polymer thickener (example 67) in comparison to otherwise comparable thickeners which, as usual, contain the hydrophilic homopolymer polyethylene glycol (examples 68 to 71). If the viscosity in water is acceptable, the thickening effect in the test binder is roughly comparable to that of the corresponding comparison substances. Table V

Polymerized copolymer PPG / PEG (1: 4) polyglycol in the thickener polymerizes similar polymers without

PPG content is 20% in water too highly viscous

Examples 72 to 75 (according to the invention)

Table VI lists examples in which combinations of pseudoplastic (A) and Newtonian thickeners (B) are additionally mixed with the plasticizers (C). This can further reduce the viscosity in water or increase the solids content of the pseudoplastic thickener.

Table VI Trimere mixtures of pseudoplastic thickeners, plus Newtonian thickeners, plus plasticizers

The compositions of the individual model thickeners are given in Table VII.

Table VII Composition of model thickeners

* Implementation without catalyst, addition instead of Powderlink 1174

Polyglycol P41 / 12000 (statistical copolymer of propylene glycol and ethylene glycol 4: 1, molecular weight 20,000, (Clariant)

Igepal CA 890 (octylphenol ethoxylate, Rhodia) Soprophor S40 (tristyrylethoxylate, Rhodia) Neodol 91-8E (C9 bis Cll fatty alcohol ethoxylate, Shell) Rhodasurf A60 (C18 fatty alcohol ethoxylate) Powderlink 1174 (Glycoluril, Cytec) The compositions of some model plasticizers are given in Table VIII.

Table VIII Composition of the model plasticizers

C10 Polyglycol Bll / 50 (monobutyl terminated statistical

Copolymer of propylene glycol and ethylene glycol 1: 1; Clariant)

Cll polyglycol B01 / 50 (monobutyl-terminated polypropylene glycol; Clariant)

C12 Pluriol P900 (polypropylene glycol, BASF)

C13 polyglycol MllOO (monomethyl-terminated polyethylene glycol, Clariant)

C14 Pluriol PE 6800 (polypropylene / ethylene glycol 3-block copolymer with 20% PPG, BASF)

C15 Poly-THF 2900 (polybutylene glycol, BASF) BDG (butyl diglycol) PEG (polyethylene glycol) PPG (polypropylene glycol) Test Methods:

The viscosities of the aqueous solution given in the tables were determined in a Brookfield RVT viscometer, at 20 rpm and 23 ° C., read off after 2 minutes of measurement.

The test system is structured as follows:

2.5 g of thickener solution are homogeneously stirred into a mixture of 100 g of Acronal 290D (styrene-acrylate dispersion, BASF), 30 g of deionized water and 0.3 g of defoamer ADDID 800 (Wacker). After 4 hours of ripening, the viscosity is determined at 23 ° C. in a Bohlin viscometer (measuring system PP 30, gap 150 μm) at the shear rates 1 sec ^"1 , 100 sec ^-1 , 10,000 sec ^""1. For reasons of simplicity, the Viscosity of the thickeners only tested in the binder alone, as experience has shown that these values are in parallel with those obtained in a test in a complete color formulation.

Claims

1. Associative thickness preparation with a viscosity in aqueous solution of less than 25,000 mPas, containing

(e) a combination of at least one pseudoplastic associative thickener (A), at least one Newtonian associative thickener (B), at least one solvent and at least one wetting agent; and or

(f) a combination of at least one pseudoplastic thickener (A) and at least one plasticizer (C); and or (g) a combination of at least one Newtonian thickener (B) and at least one condenser (C).

2. Association thickener preparation according to claim 1 (b-d), containing a pseudoplastic associative thickener (A) and a plasticizer (C), the plasticizer (C) being a condensation product of hydrophilic, water-soluble oligomeric (D) and hydrophobic components (E).

3. associative thickness preparation according to claim 2, characterized in that the liquefier (C) is a copolymer or cooligomer of alternating hydrophilic and hydrophobic molecules or a higher molecular weight ester, these substances having a boiling point> 250 ° C.

4. associative thickness preparation according to claim 2 or 3, characterized in that the hydrophobic component (E) of the plasticizer (C) is a bifunctional molecule XRX ₂ , wherein R is a saturated or unsaturated aliphatic or cycloaliphatic radical having 2 to 30 carbon atoms, preferably with 2 to 12 carbon atoms and particularly preferably with 3 to 6 carbon atoms, or an aromatic radical with 6 to 12 carbon atoms or a mixed aliphatic-aromatic radical and X and X ₂ , which may be the same or different and can react with the functional group Z or Z ₂ (a group containing an active hydrogen, such as a hydroxyl group, an amino or amido group) of the hydrophilic component (D), where X and X _{2 are} from the rest of one Carboxylic acid, a carboxylic acid anhydride, a carboxylic acid chloride, an ester, an isocyanate, an epoxy or a halogen ion.

5. Association thickness preparation according to claim 4, characterized in that the hydrophobic portion (E) represents the rest of adipic acid, phthalic anhydride or dimethyl terephthalate.

6. associative thickness preparation according to claim 3, characterized in that the hydrophilic component (D) of the liquefier (C) is an oligomer of the formula Z- [CH ₂ CH ₂ ~ 0] _m -CH ₂ CH ₂ -Z ₂ , wherein m = 1 to 15, preferably 2 to 6 and Z and Z ₂ , which are the same or different from one another, represent a group containing an active hydrogen atom, for example an alcohol, an amine or a secondary amine group.

7. Association thickness preparation according to claim 6, characterized in that the hydrophilic component (D) is selected from the group of short-chain polyethylene glycols.

8. Association thickener preparation according to claim 2, characterized in that the molar ratio between hydrophilic (D) and hydrophobic (E) fractions approximately 6: 5 to 5: 6, preferably approximately 3: 2 to 2: 3, in particular approximately 2: 1 is up to 1: 2.

9. Association thickness preparation according to one of claims 1 to 3, characterized in that the liquefier (C)

(a) copolymer of short chain polyethylene glycol and adipic acid and / or phthalic anhydride;

(b) a copolymer of ethylene glycol and propylene glycol and / or butylene glycol; (c) a random copolymer of ethylene glycol and propylene glycol and / or butylene glycol, the proportion of polyethylene being from 40 to 90 mol%;

(d) is oligomeric propylene glycol or oligomeric butylene glycol with preferably a maximum of 10 monomer units.

10. Association thickener preparation according to claim 2, characterized in that the proportion of the liquefier (C) between about 5 and 50 wt .-%, preferably between about 10 and 30 wt .-%, particularly preferably between about 15 and 25 wt .-% lies .

11. Association thickness preparation according to one of the preceding claims, characterized in that the plasticizer (C) is obtainable from the hydrophilic components (D) and the hydrophobic components (E) by polycondensation and / or polyaddition.

12. Association thickener preparation according to one of the preceding claims, characterized in that either the pseudoplastic (A) or the Newtonian (B) associative thickener or both contain a copolymer or cooligomer of alternating hydrophilic and hydrophobic structural elements in the molecule.

13. Association thickener preparation according to one of the preceding claims, characterized in that in the shear thickener (A) a copolymer or cooligomer of alternating hydrophilic and hydrophobic constituents is copolymerized, the copolymerized copolymer or cooligomer being a statistical copolymer. makes up more than 75% by weight of the water-soluble base chain of the associative thickener.

15. Associative thickener preparation according to one of the preceding claims, obtainable by polycondensation or polyaddition of PEG / PPG copolymers or cooligomers with di-isocyanates, glycolurils, aminoplasts and / or hydrophobic groups (associative thickener A).

16. associative thickness preparation according to one of the preceding claims, characterized in that the liquefier (C) is used either alone or in combination with an additional solvent and / or surfactant.

17. Association thickness preparation according to claim 16, characterized in that the solvent is butyl diglycol, butyl triglycol or hexanediol.

18. Association thickness preparation according to claim 16, characterized in that the surfactant is selected from the group of wetting agents, defoamers, dispersants, leveling agents, coalescing agents and film-forming aids.

19. A method for producing the associative thickness preparation according to one of the preceding claims, characterized in that

(a) at least one structurally viscous associative thickener

(A) dissolves in water together with at least one Newtonian associative thickener (B); (b) at least one shear thinning associative thickener

(c) at least one shear thinning associative thickener

(A) dissolves in water and adds at least one plasticizer (C);

(d) dissolving at least one structurally viscous associative thickener (A) and a Newtonian associative thickener (B) for further lowering the viscosity together with a solvent and / or surfactant in water, the dispersant and / or wetting agent being the surfactant and the solvent uses a glycol with a boiling point> 250 ° C.

20. Use of the associative thickener preparation according to one of the preceding claims for adjusting the rheology of dispersion-bound aqueous paints and varnishes or other aqueous systems from the group of cleaning agents, cosmetics, strippers, aqueous pigment pastes, car paints, industrial paints, printing inks, greases, cleaning agents and Wall paints, textile coatings, pharmaceutical preparations, crop protection formulations, filler dispersions, adhesives, detergents, ^■ wax dispersions, polishes and auxiliaries for tertiary oil production.

21. Use of the plasticizer (C) according to one of claims 3 to 9 as a coalescing agent, film binding agent or wetting and dispersing aid in aqueous systems.