DE102004058118A1 - Thickener concentrate - Google Patents

Abstract

Solvent- and surfactant-free, water-dispersible thickener concentrates consisting of (a) 1 to 98% by weight of a polyurethane associative thickener of the HEUR type, (b) 1 to 98% by weight of a polyether-type associative thickener and ( c) 1 to 98% by weight of water, the percentages by weight of the individual components being based on the composition of the entire concentrate and the sum of components (a), (b) and (c) being 100%, with the proviso that component (b) is selected from the compounds of formula (I) DOLLAR AR * 1 * ABCD, DOLLAR A wherein R * 1 is selected from 3- or 4-valent radicals of the group linear or branched aliphatic groups having 3 to 50 carbon atoms, cycloalkyl groups having 4 to 20 carbon atoms, olefinically unsaturated linear or branched aliphatic groups having 3 to 40 carbon atoms, cycloalkenyl groups having 5 to 20 carbon atoms and aromatic groups, these aromatic groups optionally with 1 to 4 linear and wherein the total number of carbon atoms of the optionally substituted aromatic groups is 6 to 21, with the proviso that within the radical R · 1 · up to four methylene groups (--CH¶2¶ -), which may not be immediately adjacent, may be replaced by an oxygen atom (-O-), DOLLAR AA is a group - (OX¶i¶-R · 2 ·) ¶n¶, B is a group - (OX ¶J¶-R · 3 ·) ¶m¶, C is a group - (OX¶k¶-R · 4 ·) ¶o¶ and D is a group - (OX¶l¶-R · 5 ·) ¶p¶ , DOLLAR A ...

Description

Field of the invention

The Invention relates to solvent-free, water-dispersible thickener concentrates of special composition.

As known to those skilled organic thickening on the Field of coating compositions, in particular the paint and varnish systems, solvent-based, on the other hand also water-based for use. This will be the viscosity, Flow behavior, Drain resistance and processing viscosity at low and high shear rates regulated. With the right choice of thickener you can the Paint system also give a certain pour point or a time-dependent flow behavior.

In Water-based paints the thickener according to the way in which the paint thicken, be differentiated. There are products that are just the water phase thicken, and system thickeners that interact through the paint give viscosity with other paint components.

at those compounds that thicken only the water phase are Cellulose ethers the most common used materials. Typically these are following product groups: cellulose derivatives, starch derivatives, acrylate thickeners. The advantage of products that paint only over the Water phase thickening is that she system independent function and the rheological behavior of the paint becomes predictable with such products. Thicken the products the water phase in two stages. The water is bound by hydrogen bonds, which only leads to a slight increase in viscosity. When increasing the Concentration becomes the viscosity by polymer chain overlap greatly increased and thus the viscosity of the paint achieved. A corresponding paint system behaves on the one hand as a viscoelastic material, thus has liquid properties, but also like an elastic material. Disadvantage of a such a thickening mechanism is that due to the dominating Effect of the elastic component, the viscosity of the paint color insufficient becomes. Thereby can Thickener for high gloss colors, which are spread with the brush, not be used. Furthermore can high molecular weight thickener for flocculation of pigment particles and binder particles with insufficient stabilization of pigment or binders contribute. This leads to a reduction of Film gloss in high-gloss colors and increased sensitivity to water the final coating. These problems turn have led to the development of system thickeners.

Under System thickeners are understood to mean organic thickeners, although to a certain extent water soluble but the paint color is due to the interaction with others Thicken the color components. It is believed that this Interactions on hydrophobic forces based. Within the group of system thickeners are usually hydrophobically modified polyoxyethylenes (HEUR), associative Acrylate thickener (HASE), associative cellulose ethers.

The hydrophobically modified polyethylene oxides are usually the expert as polyurethane thickener (PUR) or as hydrophobically modified ethoxylated urethanes (HEUR) known. Here are the mentioned Terms and abbreviations Synonyms. The first thickeners of the HEUR type were already in the seventies Launched on the market. Today they are among the most important Thickening for aqueous color and paint systems.

• • solche mit 2 endständigen hydrophoben Gruppen,
• • solche mit 3 hydrophoben Gruppen (Isocyanurat-Typen)
• • solche mit mehr als 3 hydrophoben Gruppen; es handelt sich hierbei um Polymere mit sogenannter Kammstruktur, wobei die Anordnung der Hydrophobgruppen zufällig oder blockweise sein kann.

The molecules of HEUR thickeners contain as building blocks: hydrophobic segments, several hydrophilic segments (polyoxyethylene building blocks) and urethane groups. Classification of HEUR thickeners is possible, for example, according to the number and arrangement of the hydrophobic groups. This is how the following HEUR types are distinguished:

• • those with 2 terminal hydrophobic groups,
• • those with 3 hydrophobic groups (isocyanurate types)
• • those with more than 3 hydrophobic groups; these are polymers with so-called comb structure, wherein the arrangement of the hydrophobic groups can be random or blockwise.

HEUR thickeners typically have molecular weights in the range of 10,000 to 50,000 and come in liquid form, usually as a solution or dispersion in water or in powder form in the trade.

Classical aqueous HEUR thickener were usually with a certain content of organic solvents formulated. However, this has because of the content of volatile organic compounds (VOC) disadvantages.

In It has therefore recently been proposed to use organic solvents to replace. As examples of this newer technology where the solvents are substituted by surfactants Reference may be made to EP-B-682,094 and EP-B-835,291.

Description of the invention

task The present invention was solvent-free and surfactant-free aqueous thickener concentrates to provide on HEUR basis.

The present invention relates to water-dispersible thickener concentrates consisting of (a) 1 to 98 wt .-% of a polyurethane associative thickener type HEUR, (b) 1 to 98 wt .-% of a associative thickener of the polyether type and (c) 1 to 98 % By weight of water, the weight percentages of the individual components being based on the composition of the total concentrate and the sum of components (a), (b) and (c) being 100%, with the proviso that the component (b) is selected from the compounds of the formula (I) R ¹ -ABCD (I) wherein R ^{1 is} selected from 3- or 4-valent radicals of the group of linear or branched aliphatic groups having 3 to 50 carbon atoms, cycloalkyl groups having 4 to 20 carbon atoms, olefinically unsaturated linear or branched aliphatic groups having 3 to 40 carbon atoms Atoms, cycloalkenyl groups having 5 to 20 carbon atoms and aromatic groups, wherein these aromatic groups may be optionally substituted with 1 to 4 linear and / or branched aliphatic groups and wherein the total number of carbon atoms of the optionally substituted aromatic groups is 6 to 21 with the proviso that within the radical R ¹ up to four methylene groups (-CH ₂ -), which may not, however, be immediately adjacent, may each be replaced by an oxygen atom (-O-),
A is a group - (OX _i R ² ) _n , B is a group - (OX _j -R ³ ) _m , C is a group - (OX _k -R ⁴ ) _o and D is a group - (OX _l -R ⁵ ) _P .
X is an ethyleneoxy-1,2-propyleneoxy or 1,2-butyleneoxy group,
the indices i, j, k and l independently of one another 0 or a number in the range of 50 to 200, with the proviso that at least two of the indices i, j, k and l are different from 0,
the indices n, m, o and p independently of one another each denote 0 or 1, with the proviso that at least three of the indices n, m, o and p have the value 1 and the further proviso that in the event that n, m, o or p has the value 0, the corresponding valence of the radical R ^{1 is} saturated with hydrogen, and
the radicals R ² to R ⁵ independently of one another are alkyl, aryl or alkaryl groups each having 1 to 50 C atoms.

In an embodiment contain the thickener concentrates according to the invention the following components in the following amounts: 2 to 25% HEUR thickener (a), 2 to 25% polyether thickener (b) and 50 to 96% water (c), in a preferred embodiment the sum of components (a) and (b) is 15 to 50%.

Especially preference is given to those thickener concentrates according to the invention the sum of components (a) and (b) is in the range of 20 to 40%, wherein components (a) and (b) are present in a weight ratio, which is in the range of 1:10 to 10: 1 and especially 1: 1 to 1: 5.

To the compounds (a): associative HEUR thickener

The HEUR thickener usable in the context of the present invention are not subject to any special restrictions. It's all possible the Fachman relevant use known HEUR thickener. To define the HEUR thickener be on the chapter "Stand the technique ".

To the compounds (b): associative polyether thickeners

The usable in the context of the present compounds polyether thickener are characterized by the above formula (I).

Regarding the Preparation of compounds of the formula (I) is by way of example Refer to documents US-A-5,728,895 and US-A-6,002,049.

In one embodiment, compound (I) is a substance of the following structure (Ia) NP- (EO) ₅₀ -O-CH ₂ -CH (OnC ₈ H ₁₇ ) -CH ₂ -O- (EO) ₁₅₀ -NP (Ia) in which NP is a nonylphenyl radical and EO is an ethyleneoxy group.

In one embodiment, the compound (I) is a substance of structure (Ib) NP- (EO) ₅₀ -O-CH ₂ -CH (O-CH ₂ -Ph) -CH ₂ -O- (EO) ₁₅₀ -NP (Ib) in which NP is a nonylphenyl radical, EO is an ethyleneoxy group and Ph is a phenyl group.

• • m, n, o und p jeweils den Wert 1,
• • i, j, k und l jeweils 0,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• • i, j, k and l are each 0,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

• • m, n, o und p jeweils den Wert 1,
• • i, j, k und l jeweils unabhängig voneinander Werte im Bereich von 90 bis 185,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• I, j, k, and l are each independently in the range of 90 to 185,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

• • m, n, o und p jeweils den Wert 1,
• • alle vier Indices i, j, k und l jeweils den Wert 100 aufweisen,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• All four indices i, j, k and l have the value 100,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

• • m, n, o und p jeweils den Wert 1,
• • alle vier Indices i, j, k und l jeweils den Wert 125 aufweisen,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• • all four indices i, j, k and l each have the value 125,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

• • m, n, o und p jeweils den Wert 1,
• • drei der vier Indices i, j, k und l jeweils den Wert 125 und einer den Wert 100 aufweisen,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• • three of the four indices i, j, k and l each have the value 125 and one has the value 100,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

• • m, n, o und p jeweils den Wert 1,
• • drei der vier Indices i, j, k und l jeweils den Wert 100 und einer den Wert 125 aufweisen,
• • die Reste R² bis R⁵ jeweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• • three of the four indices i, j, k and l each have the value 100 and one has the value 125,
• • the radicals R ² to R ^{5 are} each nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disub substituted benzene ring (C ₆ H ₄ ).

• • m, n, o und p jeweils den Wert 1,
• • zwei der vier Indices i, j, k und l jeweils den Wert 125 und zwei den Wert 100 aufweisen,
• • die Reste R² bis R⁵ j eweils Nonylphenyl und
• • die Gruppe R¹ den vierwertigen Rest (-H₂C)₂-HC-CH₂-Bz-CH₂-O-CH-(CH₂-)₂, wobei Bz einen para-disubstituierten Benzolring (C₆H₄) bedeutet.

In one embodiment, the compound (b) used is a substance in which in formula (I):

• • m, n, o and p are each 1,
• • two of the four indices i, j, k and l each have the value 125 and two have the value 100,
• The radicals R ² to R ^{5 are in} each case nonylphenyl and
• • the group R ^{1 is} the tetravalent radical (-H ₂ C) ₂ -HC-CH ₂ -Bz-CH ₂ -O-CH- (CH ₂ -) ₂ , where Bz is a para-disubstituted benzene ring (C ₆ H ₄ ) means.

PREPARATION

example 1

1,176.0 g (136 mmol) polyglycol E 8000 (Dow Chemikals, hydroxyl number = 13), 84.0 g (274 mmol) of Edenor Me Ri 90 (technical castor acid methyl ester; Fa. Cognis Iberia; Hydroxyl number = OH: 183; MG: 307) and 4.8 g (34 mmol) of trimethylolpropane were placed in a 1-1 four-necked flask. After evacuating and venting with nitrogen twice, vacuum became vacuum applied, the mixture to 120 ° C heated and two hours at this temperature and a pressure of drained about 10 mbar. Then it was aerated with nitrogen and the inert gas atmosphere maintained in the further course by a slight Stckstoffstrom. Now, 81.0 g (332 mmol) of m-tetramethylxylene diisocyanate (TMXDI, CYTEC) and, as catalyst, 1.2 g of dibutyltin dilaurate added and the temperature maintained at 120 ° C. The reaction became aborted, as the NCO content (starting value = 0.95%) has a value of Had reached 0%. One filled hot in a storage vessel and then left Cool room temperature. Weighing = 1250 g.

Example 2

4 g of the example 1 prepared polyurethane (associative thickener of the HEUR type) were in a Flask given, this evacuated and aerated with nitrogen. you added 60 g DSX 3075 (commercially available Associative thickeners of the polyether type in water; Solids content = 20%; Co. Cognis Corporation), heated to 80 ° C and move, until a homogeneous mixture had formed. Then you let up Cool room temperature. The result was a viscous, slightly cloudy product.

Final weight = 63.6 g; Solids content = 25%; Water content = 75%; Viscosity = 27500 mPas (Brookfield; cone / plate; 5 rpm; 20 ° C). The resulting associative thickener concentrate is free of surfactant and solvent.

applications

It were various aqueous plastic dispersions produced. These were on the one hand with the HEUR thickener according to example 1 added (Comparative Examples = Experiments 3a to 9a), on the other with the thickener concentrate according to the invention according to example 2 (Examples of the invention = Experiments 3b to 9b). Thickener according to Example 1 and aqueous thickener concentrate according to example 2 were related to the content of associative thickeners respectively used at the same level.

Examples according to the invention

Example 3b

80 g Acronal 290 D (commercial Styrene-acrylic acid polymer) and 20 g of water were mixed together. One put 0.4 g of the aqueous Thickener concentrate according to example 2 (containing 0.1 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Example 4b

75 g UCAR D 68 M (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.8 g of the aqueous Thickener concentrate according to example 2 (containing 0.2 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Example 5b

75 g Primal AS 398 (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 1.2 g of the aqueous Thickener concentrate according to example 2 (containing 0.3 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Example 6b

75 g Eternal 6512-2 (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.4 g of the aqueous Thickener concentrate according to example 2 (containing 0.1 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Example 7b

75 g Eternal 6512-2 (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.8 g of the aqueous Thickener concentrate according to example 2 (containing 0.2 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by

Example 8b

75 g Neocryl XK 90 (commercially available Acrylic acid polymer) and 25 g of water were mixed together. One put 1.2 g of the aqueous Thickener concentrate according to example 2 (containing 0.3 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Example 9b

75 g Airflex CEZ 16 (commercially available Vinyl acetate polymer) and 25 g of water were mixed together. 1.6 g of the aqueous was used Thickener concentrate according to example 2 (containing 0.4 g of solids) and 2 g of propylene glycol and 1 g Texanol and stirred good by.

Comparative Examples

Example 3a

80 g Acronal 290 D (commercial Styrene-acrylic acid polymer) and 20 g of water were mixed together. One put 0.1 g of the HEUR thickener according to example 1 and 2 g of propylene glycol and 1 g of Texanol and stirred well by.

Example 4a

75 g UCAR D 68 M (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.2 g of the HEUR thickener according to example 1 and 2 g of propylene glycol and 1 g of Texanol and stirred well by.

Example 5a

75 g Primal AS 398 (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.3 g of the HEUR thickener according to example 1 and 2 g of propylene glycol and 1 g of Texanol and stirred well by.

Example 6a

75 g Eternal 6512-2 (commercially available Styrene-acrylic acid polymer) and 25 g of water were mixed together. One put 0.1 g of the HEUR thickener according to example 1 and 2 g of propylene glycol and 1 g of Texanol and stirred well by.

Example 7a

75 g of Eternal 6512-2 (commercial styrene-acrylic acid polymer) and 25 g of water were mixed together. 0.2 g of the HEUR thickener according to Example 1 and 2 g of propylene glycol and 1 g of Te were used xanol and stirred well.

Example 8a

75 g Neocryl XK 90 (commercially available Acrylic acid polymer) and 25 g of water were mixed together. One put 0.3 g of the HEUR thickener according to example 1 and 2 g of propylene glycol and 1 g of Texanol and stirred well by.

Example 9a

75 g Airflex CEZ 16 (commercially available Vinyl acetate polymer) and 25 g of water were mixed together. 0.4 g of the HEUR thickener according to Example 1 and 2 g of propylene glycol were used and 1 g of Texanol and stirred good by.

The both test series including the determined viscosity data The thickened dispersions obtained in each case are given in Table 1 remove.

Table 1

To the columns of the table 1:

• Column 1: test number (b = according to the invention, a = zum Comparison) / column 2: type of polymer of the plastic dispersion / column 3: type of thickener / column 4: solvent = 2% propylene glycol and 1% Texanol (% by weight based on the total dispersion) / column 5: Amount of added thickener (wt .-% based on the total Dispersion) / column 6: logarithm of the Brookfield viscosity (mPas) at 6 rpm and 20 ° C / column 7: Logarithm of Brookfield viscosity (mPas) at 60 rpm and 20 ° C / column 8: logarithm of ICI viscosity (mPas) at 10,000 rpm and 20 ° C

Claims (1)

Water-dispersible thickener concentrates consisting of (a) 1 to 98% by weight of a polyurethane associative thickener of the HEUR type, (b) 1 to 98% by weight of a polyether-type associative thickener and (c) 1 to 98% by weight of water in which the weight percentages of the individual components relate to the composition of the total concentrate and the sum of components (a), (b) and (c) gives 100%, with the proviso that component (b) is selected from the compounds of the formula (I) R ¹ -ABCD (I) wherein R ^{1 is} selected from 3- or 4-valent radicals of the group of linear or branched aliphatic groups having 3 to 50 carbon atoms, cycloalkyl groups having 4 to 20 carbon atoms, olefinically unsaturated linear or branched aliphatic groups having 3 to 40 carbon atoms Atoms, cycloalkenyl groups having 5 to 20 carbon atoms and aromatic groups, wherein these aromatic groups may be optionally substituted with 1 to 4 linear and / or branched aliphatic groups and wherein the total number of carbon atoms of the optionally substituted aromatic groups is 6 to 21 with the proviso that within the radical R ¹ up to four methylene groups (-CH ₂ -), which may not be immediately adjacent, may be replaced by an oxygen atom (-O-), A is a group - (OX _i R ² ) _n , B is a group - (OX _j -R ³ ) _m , C is a group - (OX _k -R ⁴ ) _o and D is a group - (OX ₁ -R ⁵ ) _P , X is an ethyleneoxy-1, 2-propyleneoxy or 1,2 butyleneoxy group, the indices i , j, k and l are independently 0 or a number in the range of 50 to 200, with the proviso that at least two of the indices i, j, k and 1 are different from 0, the indices n, m, o and p are independent each represent 0 or 1, with the proviso that at least three of the indices n, m, o and p have the value 1 and the further proviso that in the event that n, m, o or p has the value 0, the corresponding valency of the radical R ^{1 is} saturated with hydrogen, and the radicals R ² to R ⁵ independently of one another are alkyl, aryl or alkaryl groups each having 1 to 50 C atoms.