AQUEOUS POLYMER DISPERSION FOR ADHESIVE FORMULATIONS

Abstract

The present invention relates to aqueous polymer dispersions of polymers made of polymerized ethylenically unsaturated monomers M which comprise or consist of: a) 55 to 88% by weight, based on the total weight of the monomers M, of at least one monomer Ma consisting of a1) at least one monomer Ma(1) selected from alkyl acrylates having a branched alkyl radical having 3 to 20 carbon atoms, alkyl methacrylates having a branched alkyl radical having 5 to 20 carbon atoms, where the homopolymer of monomer Ma(1) has a theoretical glass transition temperature of at most 10° C. and optionally a2) at least one monomer Ma(2) selected from alkyl acrylates having a linear alkyl radical of 2 to 6 carbon atoms; wherein the weight ratio of monomer Ma(2) to Ma(1) is at most 2:1; b) 8 to 30% by weight, based on the total weight of the monomers M, of a monomer Mb, which is a monoethylenically unsaturated carbonitrile; c) 0 to 25% by weight, based on the total weight of the monomers M, of at least one non-ionic monoethylenically unsaturated monomer Me which is different from the monomers Mb and whose homopolymer has a glass transition temperature of at least 60° C.; provided that the total amount of monomer Mb and Me is in the range of 12 to 40% by weight, based on the total weight of the monomers M; d) at most 2.0% by weight, based on the total weight of the monomers M, of one or more monoethylenically unsaturated monomers Md having an acidic group; e) at most 5% by weight, based on the total weight of the monomers M, of at least one ethylenically unsaturated monomer Me which, alone or with a crosslinking agent, has crosslinking effect and which is different from the monomers Ma to Md; f) at most 10% by weight based on the total weight of the monomers M, of at least one non-ionic monoethylenically unsaturated monomer Mf which has a water-solubility of at least 100 g/L and which is different from the monomers Me; provided that the total amount of monomers Md, Me and Mf does not exceed 10% by weight, based on the total weight of the monomers M. The polymers are suitable as polymer adhesives, in particular as polymer adhesives or binders, respectively, in aqueous flooring adhesive compositions.

Claims

1.-28. (canceled)

29. An aqueous polymer dispersion of a polymer made of polymerized ethylenically unsaturated monomers M comprising a) 55 to 88% by weight, based on the total weight of the monomers M, of at least one monomer Ma consisting of a1) at least one monomer Ma(1) selected from alkyl acrylates having a branched alkyl radical having 3 to 20 carbon atoms, alkyl methacrylates having a branched alkyl radical having 5 to 20 carbon atoms, where the homopolymer of monomer Ma(1) has a theoretical glass transition temperature of at most 10° C. and a2) optionally at least one monomer Ma(2) selected from alkyl acrylates having a linear alkyl radical of 2 to 6 carbon atoms; wherein the weight ratio of monomer Ma(2) to Ma(1) is at most 2:1; b) 8 to 30% by weight, based on the total weight of the monomers M, of a monomer Mb, which is a monoethylenically unsaturated carbonitrile; c) 0 to 25% by weight, based on the total weight of the monomers M, of one or more monoethylenically unsaturated non-ionic monomer Mc, whose homopolymers have glass transition temperatures of at least 60° C. and which are different from the monomers Mb and Me; provided that the total amount of monomer Mb and Mc is in the range of 12 to 40% by weight, based on the total weight of the monomers M; d) at most 2.0% by weight, based on the total weight of the monomers M, of one or more monoethylenically unsaturated monomers Md having an acidic group; e) 0 to 5% by weight, based on the total weight of the monomers M, of one or more monomers Me which, alone or with a crosslinking agent, have crosslinking effect and which are different from the monomers Ma to Md; f) 0 to 10% by weight, based on the total weight of the monomers M, of one or more non- ionic monoethylenically unsaturated monomer Mf which have a water-solubility of at least 100 g/L and which are different from the monomers Me; provided that the total amount of monomers Md, Me and Mf does not exceed 10% by weight, based on the total weight of the monomers M.

30. The aqueous polymer dispersion of claim 29, where the monomer Ma(1) is selected from alkyl acrylates having a branched alkyl radical having 6 to 12 carbon atoms.

31. The aqueous polymer dispersion of claim 29, where the weight ratio of monomer Ma(2) to monomer Ma(1) is in the range of 1:10 to 2:1.

32. The aqueous polymer dispersion of claim 29, where the amount of monomer Mb is in the range of 12 to 28% by weight, based on the total weight of monomers M.

33. The aqueous polymer dispersion of claim 29, where the monomer Mb is acrylonitrile.

34. The aqueous polymer dispersion of claim 29, where the monomer Mc is a vinylaromatic hydrocarbon monomer, in particular styrene.

35. The aqueous polymer dispersion of claim 29, where the monomer Mc is comprised in the monomers M in an amount in the range of 2 to 20% by weight, based on the total weight of the monomers M.

36. The aqueous polymer dispersion of claim 29, where the monomer Md is selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms.

37. The aqueous polymer dispersion of claim 29, where the monomer Md is comprised in the monomers M in an amount in the range of 0.05 to 1.5% by weight, based on the total weight of the monomers M.

38. The aqueous polymer dispersion of claim 29, where the monomer Mf is selected from the group consisting of hydroxyalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms.

39. The aqueous polymer dispersion of claim 29, wherein the monomers M comprises a monoethylenically unsaturated monomer Me which is a monomer Me(1.2) having at least one keto carbonyl group.

40. The aqueous polymer dispersion of claim 39, which contains an organic compound having at least two functional groups which are capable of reacting with the keto carbonyl group by formation a covalent bond between the carbon atom of the keto group and an atom of the functional group.

41. The aqueous polymer dispersion of claim 29, where the monomer Me is comprised in the monomers M in an amount in the range of 0.01 to 5% by weight, based on the total weight of the monomers M.

42. The aqueous polymer dispersion of claim 29, where the polymer has a glass transition temperature of at most 0° C.

43. The aqueous polymer dispersion of claim 29, where the monomers M comprise a) 55 to 80% by weight, based on the total weight of the monomers M, of at least one monomer Ma comprising a1) 25 to 79% by weight, based on the total weight of the monomers M, of at least one monomer Ma(1) selected from alkyl acrylates having a branched alkyl radical having 6 to 12 carbon atoms, a2) 1 to 50% by weight, based on the total weight of the monomers M, of at least one monomer Ma(2) selected from alkyl acrylates having a linear alkyl radical of 2 to 6 carbon atoms; b) 12 to 30% by weight, based on the total weight of the monomers M, of acrylonitrile as the monomer Mb; c) 2 to 20% by weight, based on the total weight of the monomers M, of styrene as the monomer Mc; provided that the total amount of monomer Mb and monomer Mc is 14 to 39.95% by weight; d) 0.05 to 1.0% by weight, based on the total weight of the monomers M, of one or more monoethylenically unsaturated monomers Md having an acidic group; e) 0.1 to 5% by weight, based on the total weight of the monomers M, of a monomer Me comprising a monoethylenically unsaturated monomer Me(1.2) having a keto carbonyl group.

44. The aqueous polymer dispersion of claim 43, which is formulated with a dihydrazide.

45. The aqueous polymer dispersion of claim 29, which is obtained by a process comprising a free-radical aqueous emulsion polymerization of the monomers M.

46. The process for preparing an aqueous polymer dispersion of claim 29, which comprises an aqueous emulsion polymerization of the monomers M.

47. The process of claim 46, where the monomers M comprise a monomer Md and where during the emulsion polymerization the Monomer Md is at least partly present in its anionic form.

48. A method comprising utilizing the aqueous polymer dispersion as defined in claim 29 as a polymer adhesive in an aqueous adhesive formulation having a pH of at least pH 10.

49. An aqueous adhesive formulation having a pH of at least pH 10 and containing the aqueous polymer dispersion as defined in claim 29.

50. The aqueous adhesive formulation of claim 49, further containing a tackifier resin.

51. The aqueous adhesive formulation of claim 50, wherein the tackifier resin is a tackifying resin which does not contain hydrolysable ester groups and which is selected from the group consisting of hydrocarbon resins, indene coumarone resins, phenol terpene resins, poly(vinyl alkyl ethers), polypropylene glycols and combinations thereof, or a combination of the tackifying resin and a plasticizer.

52. The aqueous adhesive formulation of claim 49 further containing a pH buffering agent for maintaining a pH of the formulation of least pH 10.

53. The aqueous adhesive formulation of claim 52, wherein the pH adjusting agent is selected from the group consisting of alkali metal ortho silicates, alkali metal siliconates, amino acids, alkalimetal phosphates, alkalimetal monohydrogen phosphates and alkanol amines.

54. The aqueous adhesive formulation of claim 49 further containing at least one filler.

55. The aqueous adhesive formulation of claim 49 containing i) 10 to 40% by weight of the polymer of the aqueous polymer dispersion, ii) 0 to 30% by weight of one or more tackifying resin or a combination of one or more tackifying resin and one or more plasticizer, iii) 25 to 50% by weight of at least one filler, iv) a pH buffering agent and optionally an alkali hydroxide in an amount sufficient for adjusting a pH of the formulation to least pH 10, where the numbers given in percent by weight are the relative amounts of the respective component, based on the total weight of the aqueous adhesive formulation.

56. A flooring adhesive comprising the aqueous adhesive formulation of claim 49.

Description

EXAMPLES

[0183] Hereinafter the following abbreviations were used: [0184] % b.w. % by weight [0185] AA acrylic acid [0186] AN acrylonitrile [0187] DV dynamic viscosity [0188] EHA 2-ethylhexyl acrylate [0189] EO ethylene oxide [0190] HDC: hydrodynamic chromatography [0191] H DC-PS: particle size determined by HDC [0192] HEA 2-hydroxyethyl acrylate [0193] n-BuA n-butyl acrylate [0194] n.d. not determined [0195] rpm revolutions per minute [0196] S styrene [0197] S.C. solids content

[0198] If not stated otherwise, the water used was deionized water.

1. Analytics and Characterization

1.1 Characterization of the Dispersions

[0199] i) Solids contents of the polymer dispersions were measured according to the standard method DIN EN ISO 3251: 2008-06. [0200] ii) Viscosity was measured in mPas according to the standard method DIN EN ISO 3219:1994 using a dynamic shear rheometer (Anton Paar DSR301)) with measuring system Z2 at 500 revolutions per second. [0201] iii) pH values of the polymer dispersions were measured according to the standard method DIN ISO 976:2016-12. [0202] iv) Particle Size Distribution of Polymer Dispersion by DLS [0203] The particle diameter of the polymer latex was determined by dynamic light scattering (also termed quasielastic light scattering) of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5% by weight at 22° C. by means of a HPPS from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321). The polydispersity index was calculated from a simple 2 parameter fit to the correlation data (the cumulants analysis). [0204] v) Particle Size Distribution of Polymer Dispersion by HDC [0205] Measurements were carried out using a PL-PSDA particle size distribution analyzer (Polymer Laboratories, Inc.). A small amount of sample of the polymer latex was injected into an aqueous eluent containing an emulsifier, resulting in a concentration of approximately 0.5 g/l. The mixture was pumped through a glass capillary tube of approximately 15 mm diameter packed with polystyrene spheres. As determined by their hydrodynamic diameter, smaller particles can sterically access regions of slower flow in capillaries, such that on average the smaller particles experience slower elution flow. The fractionation was finally monitored using an UV-detector which measured the extinction at a fixed wavelength of 254 nm. [0206] vi) Measurement of hydrolysis [0207] The dispersion was mixed with 5% b.w. of an aqueous solution of potassium silicate, and the pH of the mixture was adjusted to 11.3 by slowly adding a 5% b.w. an aqueous solution of potassium hydroxide. The mixture was stored at 50° C. for 14 days. Afterwards, the mixture was analyzed by GC. The content of free alcohols which could be evolved by hydrolysis of the respective ester groups in the monomers or polymer is compared with the GC measurement of the pure dispersion. The amount is given in % with respect to theoretical value of complete hydrolysis.

1.2. Application Testing of the Adhesive Formulations

[0208] vii) Measurement of pH value [0209] pH values of the polymer formulation were measured according to the standard method DIN ISO 976:2016-12 immediately after preparation of the formulation and after storage at 50° C. for 28 days. [0210] viii) Measurement of viscosity [0211] The viscosity was measured according to the standard method DIN EN ISO 2555:2018-9 using a Brookfield viscometer DV1 with spindle 6 (equal or less than 50 000 mPas) or spindle 7 (more than 50 000 mPas) at 20 revolutions per minutes, time of test: 60 seconds. The viscosity was measured immediately after preparation of the formulation and after storage at 50° C. for 28 days. Values are given in mPas. [0212] ix) Measurement of wet grab (also called wet tack or green strength) [0213] The formulation is applied as an adhesive with serrated strip TKB B 1 to fiber cement slabs (e.g., Eternit® 2000, 500×200 mm) in peel direction. NFC (Finett 11 needlefelt floorcovering) strips (150×50×5.2 mm) are laid into the bed of adhesive after venting for 10 minutes and are pressed down with a 2.5 kg roller by rolling back and forth three times. At time intervals (10, 20, 30, and 40 minutes), the coverings are peeled off with a peeling device, and the increase in the peel resistance (in N/5 cm) is ascertained. [0214] x) Measurement of dry grip (also called dry tack or open time) [0215] The formulation is applied as an adhesive with serrated strip TKB A2 to fiber cement slabs (e.g., Eternit® 2000, 500×200 mm) in peel direction. PVC strips (Tarkett standard 2 mm; 150×50×2 mm) are laid into the bed of adhesive after different venting times (20, 25, 30 and 40 minutes), and are pressed down with a 2.5 kg roller by rolling back and forth three times. Subsequently, the strips are peeled off with a peel instrument, and the increase in the peel resistance (in N/5 cm) is ascertained. [0216] xi) Measurement of heat resistance [0217] Cement fiberboard panels with a PVC floorcovering (adhesive bond surface 5×2 cm) were stored under standard climatic conditions (1 bar, 23.5° C.) for 14 days. They were then heat-treated at 50° C. in a forced-air drying cabinet for 30 minutes, then stressed in a hanging position with a 2 kg load. The time taken for the adhesive bond to separate is taken as a measure of the heat resistance. [0218] xii) Measurement of dynamic shear strength [0219] Blocks of oak were coated with the adhesive (coater: serrated strip TKB B3)) and adhesive-bonded overlapping one another (adhesive-bonded surface 26×23 mm) and pressed on with a 2 kilo weight for 1 minute. After the storage time specified under standard climatic conditions (1 bar, 23.5° C., 50% r.h.), the shear strength (in N/mm.sup.2) was tested in a tensile tester. [0220] xiii) Measurement of peel strength according to EN ISO 22631 [0221] The formulation is applied as an adhesive with serrated strip TKB A2 to fiber cement slabs (e.g., Eternit® 2000, 150×50×8 mm) in peel direction. PVC strips (Tarkett standard; 200×50×2 mm) are laid into the bed of adhesive after venting times of 5 min and 15 min, respectively, and pressed on with a 3.5 kg roller by rolling back and forth one time. After a storage time of 14 days specified under standard climatic conditions (1 bar, 23.5° C., 50% r.h.), the peel strength (in N/mm) was tested in a tensile tester at a peeling rate of 100 mm/min.

2. Materials Used for Preparing the Polymer Dispersions

[0222] Seed latex S1: Polystyrene seed latex having a solid content of 33% by weight and a volume average particle diameter of 31 nm—Emulsifier E1: 32% b.w. aqueous solution of a fatty alcohol polyethylene glycol ether sulphate, sodium salt [0223] Emulsifier E2: 20% b.w. aqueous solution of an ethoxylated C16/C18 alcohol having 18 EO units [0224] Defoaming agent Dl: Agitan® LF 305, available from Munzig

3. Production of the Polymer Dispersions

Example 1

[0225] A polymerization reactor equipped with a stirrer, a dosage module, a temperature control module and a reflux condenser was charged at room temperature as followed:

TABLE-US-00001 Initial charge #0 395.52 g water  1.82 g seed latex S1

[0226] In a first addition vessel was prepared feed/initiator solution #1 by mixing the following components:

TABLE-US-00002 Feed/initiator solution #1 102.85 g 7% b.w. aqueous solution of sodium persulfate

[0227] In a second addition vessel was prepared feed/emulsion #2 by mixing the following components:

TABLE-US-00003 Feed/emulsion #2 195.76 g water 131.25 g E1  30.00 g E2  1.20 g acrylic acid  60.00 g 20% b.w. aqueous solution of diacetone acrylamide 240.00 g acrylonitrile 159.60 g styrene 691.20 g 2-ethylhexyl acrylate 108.00 g n-butyl acrylate  2,66 g 25% b.w. aqueous solution of sodium hydroxide

[0228] In a third addition vessel was prepared feed/oxidation solution #3:

TABLE-US-00004 Feed/oxidation solution #3 24 g 10% b.w. aqueous solution of sodium acetone bisulfite

[0229] In a fourth addition vessel was prepared feed/reduction solution #4:

TABLE-US-00005 Feed/reduction solution #4 30.23 g 13.1% b.w. aqueous solution of sodium acetone bisulfite

[0230] The initial charge #0 was flushed with nitrogen and heated up to 85° C. under stirring with 150 rpm. Then after reaching the temperature of 85° C., 5% of feed/initiator solution #1 was fed into the reaction vessel in the course of 1 minute and incorporated by stirring at 85° C. over 4 minutes. Then, the remainder of feed/initiator solution #1 and also feed/emulsion #2 were commenced simultaneously and added in the following way, with the aforementioned temperature maintained: a.) feed/initiator solution #1: the remaining feed/initiator #1 was added over 3 h 45 min. b.) Feed/emulsion #2 was added using the following metering profile: 20 min with 105 g/h, then the dosing rate was linearly increased to 473 g/h within 10 min, and then the rest was dosed at that rate. Then, 24 g of water were added to the reactor, and the reaction vessel was stirred for an additional 15 minutes at 85° C. after which 0.6 g of D1 were added.

[0231] For chemical deodorization, starting at the same time, but from two spatially separated feeding vessels, feed/oxidation solution #3 and feed/reduction solution #4 were fed into the reaction vessel in the course of 2 hours with a constant feed rate. After 30 minutes, the temperature was lowered continuously to 70° C., over the course of 15 minutes and was then maintained at that temperature for 75 minutes with a gentle stream of nitrogen being passed through the apparatus and through an attached cold trap containing dry ice. Then, the reaction mixture was cooled down. At a temperature below 30° C., 18.75 g of a 32% strength aqueous solution of El was added to the reactor, while continuously stirring, followed by a mixture of 6 g of adipic dihydrazide in 44 g of water. Finally, the pH was slowly adjusted to pH 7.5 by addition of a 5% strength aqueous solution of sodium hydroxide. The properties of the dispersion of example 1 are summarized in table 2.

Example 2

[0232] The polymerization was carried out by the protocol of example 1 with the following amendments:

[0233] The feed/emulsion #2 contained the following components:

TABLE-US-00006 195.76 g water 131.25 g E1  30.00 g E2  1.20 g acrylic acid 240.00 g acrylonitrile 159.60 g styrene 691.20 g 2-ethylhexyl acrylate 108.00 g n-butyl acrylate  2.66 g 25% b.w. aqueous solution of sodium hydroxide

Example 3

[0234] The dispersion was prepared by analogy to the protocol of example 2. but the feed/emulsion #2 contained the monomers AA, AN, S, EHA, HEA and n-BuA in the amounts summarized in table 1. The amounts are given in parts by weight. The properties of the dispersion of example 3 are summarized in table 2.

Example 4

[0235] The dispersion was prepared by analogy to the protocol of example 1, but the feed/emulsion #2 contained the monomers AA, AN, S, EHA, HEA, DAAM and n-BuA in the amounts summarized in table 1. The amounts are given in parts by weight. The properties of the dispersion of example 4 are summarized in table 2

Comparative examples C1, C2 and C3

[0236] The comparative dispersions C1, C2 and C3 were prepared by analogy to the protocol of example 2, but the feed/emulsion #2 contained the monomers AA, AN, S, EHA, HEA and n-BuA in the amounts summarized in table 1. The amounts are given in parts by weight. The properties of the dispersion of comparative examples C1 to C3 are summarized in table 2.

TABLE-US-00007 TABLE 1 Monomers used and degree of neutralisation n-BuA EHA AN S HEA AA DAAM (20%).sup.1) Neut.sup.2) Example [g] [g] [g] [g] [g] [g] [g] % 1 108 691.2 240 159.6 — 1.2 60 100 2 108 691.2 240 159.6 — 1.2 — 100 3 578.4 319.2 206.4 7.2 19.2 4.8 — 60 4 132.0 790.8 168.0 108.0 — 1.2 60 100 C1 1050 — 120 — — 30 — 70 C2 534 510 60 36 60 — — 35 C3 510 510 60 60 60 — — 35 .sup.1)20% by weight aqueous solution of diacetone acrylamide .sup.2)degree of neutralisation, feed/emulsion #2 [%]

TABLE-US-00008 TABLE 2 Properties of the polymer dispersions of examples 1-4 and C1-C3 Example 1 2 3 4 C1 C2 C3 SC [% b.w.] 55 54,9 56,4 54,9 54,8 54.0 53.4 HDC-PS [nm] 206 201 198 229 486 281 346 DV [mPas].sup.1) 65 52 96 58 93 163 95 pH 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Example 1 2 3 4 C1 C2 C3 % hydrolysis.sup.2) n.d. 0.91 0.88 0.21 0.104 0.30 0.33 .sup.1)measured at 500 revolutions per second .sup.2)% free alcohol with respect to complete theoretical hydrolysis

4. Flooring Adhesive Formulation

4.1 Materials Used for Preparing the Flooring Adhesive Formulation:

[0237] Resin 1: plasticizer: fatty acid ester polyol with epoxy groups (Sovermol® 1055 of BASF SE) [0238] Resin 2: tackifier resin: terpene phenolic resin (Dertophene® of DRT)

[0239] pH-buffer: aqueous solution of potassium orthosilicate having a SiO.sub.2 content of about 21% b.w. and a K20 content of about 8.1% b.w. [0240] Thickener: hydrophobically modified ethoxylated urethane (Rheovis® PU 1191 of BASF SE) [0241] Emulsifier: sodium lauryl sulphate [0242] Defoamer: mixture of modified alcohols and a polysiloxane adduct (Foamstar SI 2210 of BASF SE) [0243] Dispersant: sodium polyacrylate (Dispex AA 4135 of BASF SE) [0244] Wetting agent: non-ionic wetting agent based on alcohol ethoxylate (100%) (Hydropalat WE 3185 EL of BASF SE) [0245] Filler: Calcium carbonate with average particle size d50 of 7 μm (Omyacarb 10 GU of Omya GmbH)

Formulation F1:

[0246] Formulation F1 was prepared from the components listed in the table 3. Table 3 also lists the amounts of the components by weight.

TABLE-US-00009 TABLE 3 Composition of formulation F1 Amount Ingredient [% b.w.] Dispersion of 36.50 example 1 Resin 1 4.50 Resin 2 10.50 pH-buffer 3.00 Thickener 0.70 Emulsifier 1.00 Defoamer 0.30 Dispersant 0.50 Wetting agent 0.40 Water 1.10 NaOH, 20% 1.50 Filler 40.00 Sum 100.00

[0247] With stirring, and at 23° C., the dispersion of example 1 was admixed with the thickener. Then, resin 1 and resin 2 heated to 105° C. and homogenized prior to the addition were added with stirring over the course of 15 minutes, followed by stirring for 10 minutes more. pH Buffer emulsifier, defoamer, dispersant, wetting agent, water, aq. sodium hydroxide solution were added in succession with stirring. Then, the filler was mixed in with stirring, followed by stirring for 10 minutes more.

Formulation F2:

[0248] Formulation F2 was prepared by analogy to the protocol of formulation F1, but using the dispersion of example 2 instead of the dispersion of example 1.

Formulation F3:

[0249] Formulation F3 was prepared by analogy to the protocol of formulation F1, but using the dispersion of example 3 instead of the dispersion of example 1.

Formulation F4:

[0250] Formulation F4 was prepared by analogy to the protocol of formulation F,1 but using the dispersion of example 4 instead of the dispersion of example 1.

Comparative Formulation CF1:

[0251] Comparative formulation CF1 was prepared by analogy to the protocol of formulation F1, but using the dispersion of example C1 instead of the dispersion of example 1.

Comparative Formulation CF2:

[0252] Comparative formulation CF2 was prepared by analogy to the protocol of formulation F1, but using the dispersion of example C2 instead of the dispersion of example 1.

Comparative Formulation CF3:

[0253] Comparative formulation CF3 was prepared by analogy to the protocol of formulation F1, but using the dispersion of example C3 instead of the dispersion of example 1.

[0254] The formulations F1 to F4 and comparative formulations CF1 to CF3 were tested for pH stability and viscosity stability after a storage of 28 d at 50° C.; for shear values, wet grap, dry grib and dimensional stability as described above. The results are summarized in table 4.

TABLE-US-00010 TABLE 4 Test comments F1 F2 F3 F4 CF1 CF2 CF3 pH stability .sup.1) −0.36 −0.8 −0.89 −0.57 −0.71 −0.83 −0.89 delta pH viscosity [mPas] .sup.2) −7 −16 −5 7 42 6 0 peel strength PVC, 5 min 2.12 1.75 1.92 1.35 3.17 0.39 0.73 [N/mm] PVC, 15 min 0.94 0.65 0.75 0.34 1.82 0.06 0.08 dynamic shear strength blocks of oak 1.42 1.47 1.10 0.98 0.62 0.35 0.34 [N/mm.sup.2] wet grab 40 min 18 12 9 19 8.5 15 7 [N/5 cm] .sup.1)Difference of pH after storage of the formulation at 50° C. for 28 d. Negative value indicates a decrease of pH 2)Difference of pH after storage of the formulation at 50° C. for 28 d. Negative value indicates a decrease of pH