DE3315690C2 - Process for the preparation of air-drying aqueous emulsions of urethane-modified alkyd resins and / or urethane oils - Google Patents

Abstract

Process for the production of air-drying aqueous emulsions of urethane-modified alkyd resins or urethane oils as binders for lacquers and paints. 50 to 75% by weight of a urethane-modified alkyd resin or urethane oil, which contains tertiary amino groups corresponding to an amine number of 3-25 mg KOH / g, is mixed with 25-50% by weight of an emulsifier component which is obtained by graft copolymerization of 50-75% by weight of polyethylene glycol-containing polyol esters of fatty acids with 17-45% by weight of vinyl and / or acrylic and / or methacrylic monomers and 5 to 8% by weight of α, β-ethylenically unsaturated carboxylic acids, and emulsifies the mixture after partial neutralization of the carboxyl groups in the presence of a maximum of 20% water-tolerant solvents in water.

Description

(I) 25-50 wt .- * of an emulsifier component which is water-soluble after neutralization with inorganic or organic bases, soft an acid number of 25-70 mg KOH / g, a hydroxyl number of a maximum of 40 mg KOH / g, a polyethylene glycol content of 7 to 13% by weight and a limit viscosity of 9 to 15 ml / g (measured in chloroform at 20 ° C) and which by graft polymerization

(a) 50 to 75% by weight of at least one having an acid number of less than 5 mg KOH / g Polyol ester containing polyethylene glycol with an average molecular weight between 1000 and 3000 of fatty acids, which on average have an iodine number of 140 or more with

(b) 17 to 45 wt .- *, of vinyl and / or acrylic and / or Meihacrylmonomers, which in addition to the Double compound have no further functional group and

(c) 5 to 8% by weight of ct, /} - ethylenically unsaturated carboxylic acids are obtained, and

(II) 50-75% by weight of an air-drying, urethane-modified alkyd resin and / or a urethane oil, which contains tertiary amino groups corresponding to an amine number of 3 to 25 mg KOH / g bound, and has a limit viscosity between 8 and 20 ml / g (measured in chloroform at 20 ° C),

at 50 to 100 ° C homogeneously mixed and after partial neutralization of the carboxyl groups with an organic view and / or inorganic base In an amount corresponding to an acid number of a maximum of 15 mg KOH / g and Emulsified in water in the presence of a maximum of 20% by weight of water-tolerant organic solvents.

The emulsions produced according to the invention contain only a very low volatile content Amines, preferably less than 1%, and are very stable. They show excellent plague wetting and can therefore be easily processed into high-gloss top coats or highly pigmented primers. You 5s show good flow and excellent drying, have only a low tendency to surface defects, such as crater formation or edge alignment, and give films of good durability.

It is known that urethane-modified binders are usually very poor with other binders are compatible. It was therefore not foreseeable that in such combinations an addition of the positive Properties of the components can also be achieved when using these inexpensive emulsifiable components. Surprisingly, the alkyd resin emulsions prepared according to the invention also show a particularly good one Compatibility with polymer isolates.

The emulsifier component (I) used according to the invention thus consists of a graft copolymer a PEG-containing polyol ester of fatty acids which on average have an iodine number of 140 or more with α, / 1-ethylene-unsaturated monomers, some of which also carry carboxyl groups.

The PEG-containing polyol esters (a) are by reaction of equivalent amounts of unsaturated Fatty acids, preferably from conjuene fatty acids and a polyethylene glycol (PEG) with a medium Molecular weight between 1000 and 3000 in the presence of a natural or synthetically produced

Polyol esters of fatty acids, which on average have an iodine number of mlnd. 140 and mostly isolated double bindings have fertilizing, obtained at 240 to 260 ° C. These esters have an acid number of less than 5 mg KOH / g, preferably less than 2 mg KOH / g.

Fatty acids for the reaction with the PEG are in particular those from the dehydrated walnut oil Konjuen fatty acids derived from and possibly post-treated as well as from other (!! fatty acids through Products obtained isomerization are used. However, selected fatty acids can also be used with isolated ones Double bonds, especially the oil fatty acids.

In order to achieve optimal results, the PEG used or the optionally used mixture should be used various polyethylene glycols have an average molecular weight of about 1500 ± 200. As polyol esters, on the one hand, the natural drying oils such. B. linseed oil, safflower oil or mixtures of these oils with a maximum of 15% by weight of a dehydrated castor oil, on the other hand synthetic esters of In These oils contain fatty acid mixtures with polyols, such as pentaerythritol or trimethylolpropane or the corresponding esters of tall oil fatty acids are used. In the fatty acids contained in these polyesters should at least 75% of the double bonds are present as isolated double bonds. In a mixture with the polyol esters can optionally also unsaturated hydrocarbon oils, such as low molecular weight butadiene polymers, Can also be used in proportions of max. 30% by weight. The hydroxyl number of the PEG containing ester (a) should be do not exceed 50 mg KOH / g. If only fatty acids are used, the production of these Component can also be done by the simultaneous conversion of all fatty acids old the PEG and the polyol.

Suitable monomers (b) which in the construction of Emul / .iOrkomponente (I) ^M are involved in a share of 17 to 45 wt .- *, vinyl and / or acrylic and / or Methacrylverblndungen be used, soft except Doppelblndung have no functional group. Your selection depends essentially on the desired properties which the paint films obtained from the emulsion should have.

For the universally applicable emulsions, which also allow the formulation of top coats, preferably the following composition is given:

60 to 78% by weight of monomers which are gasoline-soluble polymers with a glass transition temperature (7>) of form above 70 ° C. In particular vinyl toluene;

22 to 40 percent by weight of monomers which are benzine-soluble polymers with a glass transition temperature of below 70 ° C (preferably 20 to 60 ° C), especially η-butyl and isobutyl methacrylate.

The α, / I-ethylenically unsaturated carboxylic acid (c) is preferably, and also in a mixture of at least 50 mol », acrylic acid used. In addition, methacrylic acid and particularly favorable (with regard to wetting of the plasma) Half esters of maleic acid with monoalcohols with 3 to 8 carbon atoms, especially isopropyl malelnate be used.

Small proportions of maleic acid half-esters can also be produced by adducting maleic acid anhydride to the unsaturated fatty acids of component (a) and implementation of the anhydride structure with the corresponding Mono alcohols are introduced.

The graft copolymerization is advantageously carried out by slowly adding the mixture of monomers with about 20 wt .-% of component (a) and (from a separate addition vessel) of a peroxide to the

■ "'remaining about 80% of component (a) at temperatures around 130 ° C. The approach is then welter on Maintained 130-145 ° C until a practically complete reaction of the monomers and the desired one Viscosity limit has been reached. Monomcrenreste and optionally used solvents' verden Im Vacuum removed and the approach, if necessary, with approx. 10'A. a water tolerant solvent, e.g. B. a glycol ether, diluted.

· »? Particularly suitable initiators for the graft polymerization are peroxides, such as Dl-tert-butyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide or dlcumene peroxide.

The urethane-modified alkyd resins and / or urethane oils which are used as component (II) in the Emulsions used are water-insoluble resins that differ from the well-known, In organic Products dissolved in solvents and used as lacquer binders essentially through a content

> <) differentiate between bound tertiary amino groups. In terms of weight, they form the main component of the solid resin casing of the emulsions according to the invention and therefore have a decisive influence on the image and film properties. In their formulation, the main focus is therefore on quick drying and good oxidative properties Flmnetzurig laid. The task of the amino groups is to ensure compatibility with the acidic emulsifier resin to promote. You thus expand the general washing space and improve emulsion stability and fluidity.

^ Quality. In addition, the salt-like bonds with the carboxyl groups also contribute to the water compatibility at, so that the content of volatile amines, which pollute the environment when paint is used, accordingly can be lowered. Surprisingly, the water tank of the backflows is not impaired as long as it is

the amine number does not exceed 25 mg KOH / g.

The urethane-modified alkyds preferably used for the emulsions according to the present invention

^(lfl resins and urethane oils are characterized by the following key figures:

Content of unsaturated oil fatty acids: 45-70% Content of aromatic or cycloaliphatic monocarboxylic acids: 0-20% Polyalcohol content: 15-25%

<>> content of dicarboxylic acids: 0-169i,

Diisocyanate content 8-25% Hydroxyl number: 0-80 mg KOH / g

Limiting viscosity number [η]: 8-16 ml / g (chloroform, 20 "C)

The numbers given are, insofar as they concern the Amlnnummer and the Grenzvlskosiläiszahl, for the emulsions according to the present invention are critical. The other parameters specified are In yours preferred ranges indicated and can also be varied within wider limits.

Unsaturated fatty acids are those with isolated and conjugated double bonds with an iodine number but 125 suitable. Examples are: soy, safflower, lincin or tall oil fatty acids and the fatty acids in wood oil. the Fatty acids can be used freely or in the form of their glycerol oils or synthetically produced polyol esters will. The choice of aromatic or cycloalphatic monocarboxylic acids, polyalcohols and iu Dicarboxylic acids is not critical and can by the person skilled in the art on the basis of the desired properties and Key figures are taken.

In the interests of drying speed and film hardness, aromatic diisocyanates are primarily used Products such as 4,4'-diphenyl methane di-cyanate and toluene di l isocyanate are suitable. The technical one is preferred Mixture of 80% 2,4- and 20 * 2,6-Toluylendllsocyanal used.

To introduce the tertiary amino groups, amines of the general formula

YR ₁ -N

R ₃

used, where Y is a hydroxyl or a primary or secondary amino group, R is an alkylene radical with 2-5 carbon atoms and Ri and Ri denote an alkyl radical with 1-4 carbon atoms. The amount of amine is chosen so that after the reaction with the diisocyanates !! a number between 3 and 25 is preferred between 5 and 15 mg KOH / g results.

The urethane-modified binders are produced in two steps: First, according to the usual Methods a low molecular weight, hydroxylrelic alkyd resin with an acid number below 5 mg KOH / g or a Fatty acid polyol partial esters produced. Then an inert solvent is added and the at 40-60 ° C Dllsocyanat added. The mixture is kept at 60-80 ° C. until the content of free NCO groups Has fallen to around half of the theoretical starting value. The amine is then diluted with a little inert solvent, added and the temperature increased to 90-110 ° C. This temperature is held until the NCO content has fallen below 0.1% and the desired limit viscosity has been reached.

In a particular embodiment of the invention, components (I) and (II) are subjected to an aftertreatment prior to emulsification, which further improves both the drying rate and, _in particular, the surface drying (tackiness) and the cold resistance of the emulsions.

This aftertreatment consists in that component (I) at 80 to before emulsification in water 160 ° C, preferably 100 to! 50 ° C, optionally in the equivalent of a dry substance, e.g. B. a Kolbalt salt Treated with air until a peroxide value of at least 20 milllvalents per kilogram and one Increase in the limiting viscosity number (CHCIj, 20 ° C) by at least 1 ml / g is reached and / or the mixture of components (I) and (II) with 1.5 to 10 Mlllimol / 100 g of the resin mixture of an aromatic and / or aliphatic diisocyanate in the presence of an inert solvent and optionally the solvent removed from the reaction mixture by distillation prior to neutralization and emulsification.

The two measures can each be carried out individually, but also one after the other. By the Blowing with air at 80 to 160 ° C will, on the one hand, improve the drying speed (in particular surface drying), which is attributed to the formation of hydroperoxide groups can be; on the other hand, this measure also improves the compatibility, especially with short oil and high molecular weight resins of component (II) as well as, to some extent, cold resistance of the aqueous emulsions.

The reaction of the mixture of components (I) and (H) with 1.5 to! 0 Mlllmol (per 100 g of Mixture) of an aromatic and / or aliphatic Dilsocyanat causes a molecular linkage substantial improvement in the stability of the emulsions. This modification is of course only possible if the components have a minimum number of hydroxyl groups, which either from the Resin formulation originate or can be secondary to air bubbles. Preferred catfish this modification is used for products with a hydroxyl number of approx. 20 or more.

Cold resistance of the emulsion is understood to mean that the properties of the emulsion also change Repeated cooling below the freezing point of the water and reheating to room temperature is practical Don `t change. While the emulsions still cool to -5 ° C without aftertreatment If it has no effect, the emulsions after-treated according to the methods described below can be used at temperatures as low as -20 ° C can be cooled and reheated without adverse effect.

Blowing with air takes place after the completion of the graft copolymer and any removal of any existing solvent or the residues of monomers at 80 to 160 ° C, preferably at 100 to iäfrC. The bubbling (or sucking in) of air through the reaction mass is continued until the peroxide number (determined according to Wheeler) is at least 20 waste equivalents per kg and the limit viscosity number, measured in chloroform at 20 ° C, increased by at least 1 ml / g. To speed up the Process can also be small amounts of a commercially available dry substance, for example 0.02% of a 5% Co-Slccatlv solution can be added.

33 15 690 exhibit: 35-70% P.
Sl /, 0-25% 1 When using the post-treatment method, urethane-modified alkyds can also be used as component (11) 15-30% i Resins or urethane oils are used, which have extended limit values 0-20% ■ -? \
P. Content of unsaturated oleic fatty acids: 8-25% % Content of aromatic or cycloalphatic monocarboxylic acids: 3-25 (preferably 5-15) mg KOH / g Wl Polyalcohol content: below 5 mg KOH / g U Content of dicarboxylic acids: 0-100 mg KOH / g Diisocyanate content 8-20 ml / g, (chloroform, 20 ° C) Amount: S. Acid number: 1 Hydroxyl number: I. ürenzvlskosltatszahl [η]

In this case, too, the specified number ranges, insofar as they include the number and the borderline population

i ^; number are critical for the emulsion according to the present invention. The other parameters given are given in their preferred ranges and can also be varied within further limits.

To achieve emulsions with optimum cold resistance, the components can be added before emulsification be partially linked with an aromatic or aliphatic diisocyanate. Preferably will Toluylendllsocyanat used, the amount being measured so that on the one hand the desired effect

- '"is achieved, on the other hand, other properties, such as the wetting of the plague, are not impaired 1.5 to 10 millimoles of diisocyanate can be used per 100 g of resin. The preferred rate is Amount of 2 to 6 millimoles of diisocyanate per 100 g of resin.

The reaction of the mixture of components (i) and (II) with the diisocyanate takes place in an inert Solvent, ζ. B. uromatic hydrocarbons or ketones at 80 to 120 "C. After completion

- the reaction, which can be determined by the fact that the Grenzvlskosltätszihl, the solvent is under Vacuum removed.

The carboxyl groups of the mixture or the aftertreated combination of components (I) and (11) is optionally after careful removal of the water-insoluble solvents in vacuo and addition of auxiliary solution media in an amount of a maximum of 20%, based on the solid resin shell, sometimes with a

- ¹ "inorganic or organic base neutralized.

Alcohols and ethereal alcohols are suitable as auxiliary solvents; The monobutyl ether is preferred Ethylene glycol. Triethylamine and are preferred for partial neutralization of the carboxyl groups Dimethylethanolamine or mixtures of these amines, optionally also with other amines, are used. For certain purposes, ammonia or an alkali hydroxide, preferably Kalumhydro-

o xld, can be used for neutralization. One advantage of the emulsions according to the invention is that only sip.s gsrlngs Arriir.msrige, corresponding to dsr Nsusrsüssücr *. by msxlrris! ! 5 SSurszshlsiRhciicn, required! will.

It follows that the content of volatile amines in the emulsions according to the invention is less than I wt .-%

can be held.

Finally, at a temperature between 40 and 6O ⁰ C, the water under vigorous stirring in the course

• Stir in for 1 to 3 hours. Milky ones emerge. In a thin layer, transparent emulsions with good Storage stability. They can be used as quick-drying primers and top coats without any particular problems to process. The application can be in pigmented or unplgmentlcrtcr form, if necessary after the addition of the the usual paint lubricants. by painting. Diving, spraying, flooding, etc. take place. The drying takes place at Room temperature; for industrial paintwork, forced drying is preferred.

- ^; The following examples are intended to illustrate the invention. All parts or percentages relate to weight units, unless otherwise stated. The stated limit viscosity numbers were determined in chloroform (CHF) at 20 ° C. and stated in ml / g.
Explanation of the abbreviations used in the examples

> "VT: vinyl toluene

ST: styrene

MMA: methyl methacrylate BA: n-butyl acrylate BMA: n-butyl methacrylate

55 IBMA: isobutyl methacrylate

MACS: methacrylic acid ACS: acrylic acid MIPE: maleic acid monosopropyl ester MBE: mono-n-butyl malelate

<· "BUGL: ethylene glycol monobutyl ether

TDI: toluene isocyanate (commercially available mixture of 2,4- and 2,6-isomers (80:20 «) DMEA: dimethyl ethanolamine DAPA: diethylamine propylamine TlA TriäihjiiiiTiiii

- "·! '/ !. Urcn / .vlsknsUBls / ahl. CIII72 (rc, ml / g

AN: acid number, mg KOH / g OHN: hydroxyl number, mg KOH / g FKP: solids content (%)

I. Production of the emulsifier component (1) 1.1. Preparation of the PEG-containing polyol esters (a).

The raw materials given in Table 1 are heated to 250 ° C. and the reaction water is removed a / eotropically Esterified to an acid number below 2 mg KOll / g.

Table I. 1 800 56 - 150 - 0.3 2 680 120 - 56 - 150 - 0.3 3 640 160 - 56 - 0.3 4th 56 - 150 - 0.3 5 6th 780 75 - 0.3 7th 852 41 - 110 0.3 - - - - - - - _ - - _ - - - - - linseed oil - 1002 - 1002 - 150 1002 800 1002 - - 200 1000 - - 1000 Safflower oil - - - - - dehydrated - - - - - castor oil - - low molecular weight - - - Polybutadiene ¹ ) - 790 Tall oil fatty acid ² ) - dehydrate Castor oil fatty acid - Linseed oil fatty acid 110 Pentaerythritol 90 PEG (M 1500) 30th PEG (M 1000) 30th PEG (M 3000) 0.3 Dibutyl tin oxide (Catalyst) 999 Yield approx. ³ )

') Liquid polybutadiene with a viscosity of approx. 0.5 Pa · s / 20 ° C. and a cis fraction of approx. 80%.

') Commercial TallölfelUaurc with a liamic acid content of less than 2%; Iodine number approx. 150.;, <

¹ J - sowing / minus reaction water.

1.2. Graft polymerization of the polyol ester (a).

In a suitable Rcaktlonsgefäß 80% of the polyol (a) about and heated to 13O ⁰ C. The remainder of this component -vlrd mixed with the monomers was added uniformly in about 6 hours, a mixture of 3 parts of tert-butyl perbenzoate and 7 parts of xyiol being run in at the same time from a separate addition vessel (these quantities relate to the approaches given in Table 2). After the addition has ended, the temperature is increased to 140 ^° C. and this temperature is maintained until a solid

§ body of more than 90% and the desired limiting viscosity number [η] CHF, 20 ° C is reached 1st. If necessary · <

ψ, is corrected with more peroxide. The unreacted monomers or the existing

\} \ dene solvent removed by vacuum and the batch with BUGL to a solids content of 87%

ρ dilutes.

^{Table 2}

§ 123456789 10 11 12

70 - - - - 70 70 60 - - 70 70

50 ω

15 15 15 15 12 10 14 25 25 15 15 15

1 al a2 I. a3 ! - ■? ■ - a4 I. a5 I. a6 a7 i VT S. ST 1 MMA

15th M. 1 - 2 7th 10.5 3 4th 9.9 33 5 15 690 9 7th K) 8th 9 10 Il 12th continuation sz 9 - 39 _ _ 37 - - _ _ 9 _ _ OHZ - - - 9 ► 12th 6th - 3 10 K) - 9 9 ⁵ BMA 4th 4th - - - 4th 3 - - - - - IBMA 2 2 4th 4th 4th 2 - 5 6th 4th 4th 4th MACS - - 2 - 2 - - - - 2 2 2 ! "ACS Key figures - 2 - 2 2 - - - MIPE 10.3 of the components (I) 10.0 10.8 MBE 38 12.5 11.8 38 43 10.6 12.6 10.1 14th 10.4 < 36 37 45 53 36 39 39 <5 26th - <5 - ►

The composition of component I / 11 corresponds to component 1/1, but [η] was raised to a value of 14 ml / g through further additions of peroxide.

Component 1/12 also corresponds in its composition to component I / l, which became MIPE but built in by adduction. The polyol ester was mixed with the corresponding amount of malic acid - anhydride reacted for 2 hours at 220 ° C and the anhydride structures then at 90 ° C for 4 hours opened with isopropanol. The further process steps were carried out as in the production of the component I / l.

2. Production of the urethane-modified binders (II)

The composition and constants of the urethane-modified alkyd resins or urethane oils are taken from Table 3 can be found.

.κ table 3

II / l II / 2 11/3 11/4

Part 1

Tall Oil Fatty Acid - 500 510 Isomerized linoleic acid *) - 150

Safflower oil 300

Castor oil (D.C.O.) 120

Linseed oil 32 s **) - - - 346

Pentaerythritol 86 204 204 41 Trimethylolpropane 9 - - 13

> o Benzoic acid 8 - - -

p-t-butylbenzoic acid - - 90 -

Kabium octoate (4% Ca) 1 0.3 Lead octoate (10% Pb) 0.5-0.15

Part 2

Phthalic anhydride 90 90 100

part 3

TDI 82 165 154 106.5

Part 4 DMEA ^(S DAPA

TDI content (%)

19th - 15.3 !8th - 15.1 8.5 - 10.2 20.7 11.9

continuation

H / 1 H / 2 H / 3 11/4

AminesafcJ (mg KOH / G) 6.1 10.9 11.1 10.3 Limiting viscosity number [η] (CHF) 13.1 9.9 11.1 10.9 Solid approx. 91% 91% 91% 91%

*) Linoleic acid technically conjugated with approx. 50%., j

**) Thermally polymerized «linseed oil (Visit. 32 s DIN 53 211/20 ° C)

The urethane-modified binders are produced according to the following process: At U / 1 to 11/3 becomes from Part 1 and 2 by esterification at 220 ° C a low molecular weight alkyd resin with an acid number below 2 mg KOH / g produced. Bel H / 1, the oils used in Part 1 must be added to Part 2 with the polyalcohols be transesterified. This is done by heating part 1 to 250 ° C until a sample is 1: 6 with ethanol diluted, is clearly soluble at 20 ° C. With U / 4, part 1 is transesterified, as with II / 1.

The conversion of the intermediate products obtained in this way with the isocyanate and the amine takes place in one 70% solution in toluene. The preliminary products, dissolved in 90% of the required toluene, are heated to 50.degree warmed up. Then the TDI is added and the solution is heated to 70 ° C. It is now held at 70 ° C until one Control sample shows that the content of free NCO groups is about 50% of the theoretical starting value Has fallen. Then the DMEA or the DAPA, diluted with the remaining toluene, is added and the Temperature increased to 100 ° C. This temperature is maintained until the NCO content has fallen below 0.1% and the desired viscosity limit is reached. If necessary, small amounts of TDl are added. The toluene is then distilled off under vacuum to such an extent that the resin has a solids content « of about 80%. 10 parts of ethylene glycol monobutyl ether per 100 parts of solid resin are then added and further distilled under vacuum until the toluene is completely removed.

Examples 1 to 15

The composition and constants of the emulsion according to Examples 1 to 15 are summarized in Table 4 below. The viscosity of the emulsions was measured using a BROOKFIELD RVT rotary viscometer, spindle 6, 100 U / ml. measured at 20 "C.

1 2 1 46 3 './1 2 34.5 3.5 3 46 3 j 4th 3 5 3 Xk 6th 3 7th 0.5 8th 3 9 3 IO 5.5 11th 5.5 MMBHI
',/1 5.5 flBMBi 3 wmmmm 5.5 wm-mnm mmmmmmam Table 4 2 3 - 1.44 - 1.44 - 1.44 _ 1.44 _ 1.44 _ 1.44 _ 1.44 _ 1.44 _ 1.21 1.44 _ 1.80 1.44 1.44 1.44 example 3 4th - 0.64 - 0.64 - 0.64 46 0.64 - 0.64 - 0.64 - 0.64 - 0.64 - 0.53 10 0.64 - 0.79 12th 0.64 13th 0.64 14th 0.64 15th Comp. (I) 4th - 105 - 105 - 105 - 105 46 105 - 105 - 107.5 - 105 - 105 _ 102.5 - 102 - 102.5 _ 105 _ 102.5 46 5 - 9.6 - 10 - 9.7 - 9.6 - 9.6 46 9.7 - 9.5 - 9.4 - 9.3 - 9.7 - 9.9 - 9.4 - 9.7 - 9.7 - 6th - 3.2 - 1.5 - 3.6 - 2.9 - 3.9 - 2.6 46 3.7 - 2.5 - 2.9 - 3.1 - 5.2 - 1.4 - 3.8 - 3.5 - 7th - 6.75 - 6.75 - 6.75 - r., 75 - 6.75 - 6.75 - 5.65 46 6.75 - 6.75 - 7.9 - 7.9 - 7.9 - 6.75 - 7.9 - 8th - - - 0.94 - - - - - 46 0.87 - 0.94 - 1.17 - 0.94 - 0.94 - 0.94 - 9
10 S. - - - - - - - - - - - - - - - 11th - - - - _ _ - - - 57.5 - - - - 12th _ _ _ - - - - - - 46 - - - - - _ - _ _ - _ 46 - - OJ
OJ COMP. (II) 1 - - - - - 46 - - 66 77 - - - - 66 66 - _ - 46 _- - - 66 - - - - - 66 - as - - - 66 66 66 - - - - 55 66 - - - vo
O BUGL - - - - - - - - - 66 66 - TEA 66 - - - - DMEA - - - - 66 H ₂ O 3 pH 1.44 VISK Pa 0.64 BUGL% 105 AMIN% 9.7 4.1 6.75 0.94

The production of the emulsions is carried out as follows: Emulgalorkomponenie (I), urethane module. Binder (II) and BUGL are mixed well for 60 minutes at 80 ⁰ C. The temperature is then lowered to 60 ° C. and the mixture of amines is stirred in. After 30 minutes, the addition of the water is started. The water is added over the course of 60 to 90 minutes with vigorous stirring, the temperature being kept between 60 and 50 ^° C. The mixture is then stirred for a further 30 minutes. These approaches result in a solids content of 45%.

Testing of the emulsions according to Examples I to 15

1. Examination of the storage stability

To shorten the test duration, the emulsions are diluted to 305b and stored at 70 ° C. There is though no secure key, according to which from the result of this test on the storability under normal conditions can be closed. Experience teaches, however, that emulsions which under these conditions survive a week, can be stored for at least 1 year under normal conditions. The emulsions υ according to Examples 1 to 15 showed no change after this test.

2. Testing of white paints

The emulsion «? verden mixed with 2% of a water-compatible Slkkativgemlsches (e.g. with 5% Co) and 1% of an anti-skin agent (each based on solid resin) and diluted with deionized water to 35%. Then they are pigmented with titanium dioxide in a vibrating mill ("Red Devll") in a pigment binder ratio of 1: 1. After the lacquer has been applied to glass strips, the drying, gloss and water resistance of the film are tested at a dry film thickness of 30 μm. When testing the water resistance (24 hours of water storage at 20 ^° C. after 7 days of drying at room temperature), the products according to Examples 1 to 15 consistently showed a slight softening. The lzoke regenerate after a short period of time without loss of gloss.

The drying is checked with a »BK-Drylng-Recorder« (The Ml (SiIe Laboratory Engineering Co, England).
Course: Beginning of a permanent needle track ( V in minutes)

Dried up: needle mark on the film surface (A in minutes) ^M Dried through: E.ide of the needle trace visible to the naked eye (D in hours)

The gloss test is carried out using a G-Miloreflectometer »GR-COMP« (Paar, AT); Measuring angle 60 ^s . Specification: S versus standard.

Table 5 Results of testing drying and gloss

example Drying A. O shine V 120 6th 1 45 90 3.5 78 2 30th 105 5.5 69 3 50 135 5 80 4th 55 105 4.5 75 5 50 150 7th 70 6th 60 150 6.5 72 7th 50 105 5 70 8th 45 105 5.5 65 9 45 90 3.5 75 10 35 90 4th 69 11th 35 150 6.5 65 12th 50 75 3 76 13th 30th 150 6th 68 14th 50 90 4.5 74 15th 35 77

3. Examination of a corrosion protection base on the basis of the emulsions according to the invention

222 parts of emulsion according to Example I / 45 ¹ JUg are ground with 50 parts of iron oxide red, 50 parts of Blelslllcochromat, 70 parts of barlum sulfate and 30 parts of talc in conventional catfish and, after the addition of 2 parts of Co-Slkkatlv, I part of anti-skid oil, 1 part of anti-settling agent and 1 Part of the defoamer on the Rotothlnner diluted with water to a viscosity of 4 mPas (approx. 64% solids content). The pH is increased with TEA

9.0 to 9.5 adjusted.

When stored for 4 weeks at 40 ° C, the color shows no change. The TrocknungsprOfung on BK-Drylng recorder showed the values 30/75/3 for VIAID. In the salt spray test (ASTM B 117/64), films that have been dried for 7 days at room temperature show no rust under the surface after a test period of 120 hours - ^s cross section; the detachment at the cross cut was 1 to 2 mm.

Production of the emulsions with post-treated resin combinations
1. Production of the emulsifier component (I)

1.1. 800 parts of linseed oil, 56 parts of dehydrated castor oil fatty acid, 150 parts of PEG (M 1500) become In The presence of 0.3 parts of di-butylznnoxld at 250 "C with azeotropic separation of the water of reaction Polyol esters with an acid number of less than 2 mg KOH / g are produced.

1.2. 560 parts of this polyol ester (1.1.) Are placed in a suitable reaction vessel and heated to 130.degree heated. For this purpose, a mixture of 140 parts of the polyol ester (1.1.), 150 parts is added within about 6 hours Vinyltoluene, 90 parts of isobutyl methacrylate, 40 parts of acrylic acid and 20 parts of monosopropyl malelate and, from a second addition vessel, a mixture of 30 parts of tert-butyl perbenzoate and 70 parts of xylene admitted. When the addition is complete, the temperature is increased to 140 ° C. and this temperature is maintained. up to a solids content of more than 90% and a Grenzvlskosltätszah! /; (CHF, 20 ° C) of 8.8 ml / g is reached.

μ If necessary, it is corrected with additional peroxide. Then the non-reagent> ionomers or the solvent present is removed by vacuum.

The end product has an intrinsic viscosity // of 8.8 ml / g, an acid number of 37 mg KOH / g and a hydroxyl number of less than 5 mg KOH / g.
1.3. Bubbles with air. The reaction product from 1.2. is used with 0.02% of a 5% solution (based on meta

T-- halt) of a commercially available co-octoate and heats it to 130 ° C. Then air is blown through the mass until a peroxide number of 45 and a viscosity limit of 10.2 ml / g is reached; the acid number is 35 mg KOH / g (emulsifier component I / l).

Another approach is blown under the same conditions until a peroxide number! of 4? and a limiting viscosity number of 13.0 ml / g is reached; the acid number in this case is 33 mg KOH / g. The solid state

- The ¹¹ 'content is 100% in both approaches (emulsifier component 1/2).

2. Production of urethane-modified binders (component II)
. "Composition and constants can be found in Table 6 below.

Table 6 Component (II) U / 1 11/2 II / 3 U / 4

Part 1

Tall oil fatty acid 280-280 260 Linseed oil fatty acid - Benzoic acid

Glycerin 138

Trimethylolpropane -

Part 2

Phthalic anhydride 100 100 100 100

part 3
"Tolylene diisocyanate (TDI) 125 130 128 133

Part 4

Dimethylethanolamine (DMEA) 10.4 10.5 11 11

'' "Content of

TDI (%) 20.0 20.7 19.4 20.0

Fatty acids (%) 45 44.6 42.5 39

, "Solids approx.% 60 60 60 60

Intrinsic viscosity, ml / g 12.3 16.4 10.8 12.5 Amine add !, mg KOH / g 10.5 9.9 10.2 10.1

280 - - - - 20th 138 70 70 _ 100 100

The urethane-modified binders are produced according to the following process: A low molecular weight alkyd resin with an acid number below 2 mg KOH / g is produced from parts 1 and 2 by esterification at 220 ° C 60% solution in toluene. The precursors, dissolved in 90% of the required toluene, are heated to 50 ° C. Then the TDl is added and the solution is heated to 70 ° C. It is then maintained at 70 ° C. until a> Control sample shows that the content of free NCO groups has fallen to about 50% of the theoretical starting value. The DMEA, diluted with the remaining toluene, is then added and the temperature is increased to 100 ° C. The temperature is maintained at this temperature until the NCO content has _{fallen below O 1} K and the desired viscosity limit is reached Shares of TDl yielded.

3. Linking of components (I) and (II) with TDI

In accordance with the proportions given in Table 2, the components are heated to 50.degree warmed up. After adding the TDI, the temperature is increased to 100 ° C. The reaction is after 6 hours completed. The constants are listed in Table 7. is

Table 7 > ■> /! m / 2 St. / 3 1II / 4

35 0.3 38 0.6 40 40 0 108 - - 100 - 103 - - - - 100 - 0.4

Component I / 1 Component 11/1 Component 11/3 Component U / 4 TDI

Solids content% 70 71 71.5 72 Size / viscosity number ml / g 13.1 12.5 12.9 14.8 jo Millimoles of TDI per 100 grams of resin 1.7 3.5 2.3 4.0 Examples 16-20

The composition and constants of the emulsions according to Examples 16 to 20 are in the following Table 8 summarized. The viscosity of the emulsions was measured using a BROOK-FIELD rotary viscometer RVT, spindle υ, ivw vj / iTiin. i / 6i ** / ν- measured.

The combinations of components (I) and (II) are heated to 100 ° C and about half of the existing toluene distilled off under vacuum. After adding the BUGL, the remainder of the toluene is distilled off. After cooling to 60 ° C., the amines are added. After 30 minutes with the addition of the water began. The water is added over the course of 60 to 90 minutes while stirring vigorously, keeping the temperature between 60 and 50 ° C. The mixture is then stirred for a further 30 minutes. It results in these Approaches a solids content of 45%.

Table 8 jv

Example 16 17 18 19 20

Component 1/2 40 - 9.9 - - - 10.1 - - 9.9 - - - 9.8 - Component 11/2 100 - 3.2 - - - 4.9 - - 5.2 - - - 6.1 - Combination HI / 1 - - 143 - - - - Combination Hl / 2 - - 141 - - Combination HI / 3 - - - 140 - Combination III / 4 - - - - 139 toluene 40 43 41 40 39 BUGL 15th 15th 15th 15th 15th TEA 1.44 - - DMEA 0.64 - - water 105 - - PH value 10.4 Viscosity, Pa - s 3.8 BUGL% 6.75 Amine% 0.94

13th

Testing of the emulsions according to Examples 16 to 20

The emulsions were, as in Examples I to 15, on storage containers, drying, and in one White lacquer checked against corrosion resistance. Show against the test data given there the products according to the present invention show no significant differences. Major improvements On the other hand, with regard to the cooling capacity of the emulsions and the surface drying of the films achieved.

Testing of resistance to cold

The emulsions are stored for 16 hours at -23 ° C. and after a further 8 hours of storage at low temperature (22 ° C) Judged in terms of their properties. An emulsion according to Example I is used as a comparison.

The emulsions according to Examples 17 to 20 show no change, even if the Gcfrler-Tau cycle is repeated.

The emulsion according to Example 16 (without TDI linkage) shows perfect resistance to cold down to -15 ³ C, while the comparative experiment with the emulsion according to Example I already coagulates irreversibly at -8 ° C.

Testing of glue drying

White varnishes are produced from the emulsions. The emulsions are mixed with 2% of a water-compatible Co-Slkkatlvgemlsches with 5% Co and 1% of an Antlhauimlltcls (each based on the solid resin) and diluted to 35 ¹ A. with delonized water. Then they are pigmented with titanium dioxide in a vibrating mill ("Red Devil") in the plagement mixture ratio I: I. The lacquers are applied to glass strips with a dry film thickness of 30 μm. For Examples 16 to 20, a dead time of 1 to 2 hours results. With the Verglelchsbelsplel (according to Example I = without aftertreatment) the result is a period of 3 to 4 hours.

Claims (8)

Patent claims: 1. A process for the preparation of Iu ft drying emulsions of urcthanmodlflzlerten alkyd resins and / or urethane oils, characterized in that one
5 (I) 25-50 wt .- * one which is water-soluble after neutralization with inorganic or organic bases Emulsifier component, which has an acid number of 25 to 70 mg KOH / g, a hydroxyl number of maximum 40 mg KOH / g, a polyethylene glycol content of 7 to 13% by weight and a limit viscosity from 9 to 15 ml / g (measured in chloroform at 20 ° C) and which by graft copolymer 10 station (a) 50 to 75% by weight of at least one having an acid number of less than 5 mg KOH / g Containing polyethylene glycol with an average molecular weight between 1000 and 3000 Polyol esters of fatty acids which have an average iodine number of 140 or more with (b) 17 to 45% by weight of vinyl and / or acrylic and / or methacrylic monomers, other than the is double bond does not have any further functional group, and (c) 5 to 8% by weight of α, / I-ethylenically unsaturated carboxylic acids are obtained, and (II) 50-75% by weight of an air-drying, urethane-modified alkyd resin and / or a urethane oil, which contains tertiary amino groups, corresponding to an amine number of 3 to 25 mg KOH / g bound and has an intrinsic viscosity between 8 and 20 ml / g (measured in chloroform at 20 ° C) mixed homogeneously at 50 to 100 ° C and after partial neutralization of the carboxyl groups with an organic one and / or inorganic base In an amount corresponding to an acid number of a maximum of 15 ing KOH / g, and in the presence of a maximum of 20 wt .- * water-tolerant organic solvents, in water emulsifies. 2. The method according to claim 1, characterized in that the polyethylene glycol used or the Mixture of polyethylene glycols has an average molecular weight of 1500 ± 200. 3. Process according to claims 1 to 2, characterized in that in component (Ia) to replaced to 30 wt .-% of the polyol ester used by an unsaturated hydrocarbon oil. 4. Process according to claims 1 to 3, characterized in that there is used as monomers without further functional groups (b) mixtures of 60-78% by weight of monomers, which are gasoline-soluble polymers with a glass transition temperature (7 »of form above 70 ° C, and 22-40% by weight of monomers which form benzine-soluble polymers with a glass transition temperature (Tg) of below 70 ° C. are used. 5. Process according to claims I to 4, characterized in that urethane modules are used as component (II) Alkyd resins and / or urethane oils are used, which are characterized by the following key figure ranges Marked are: Content of unsaturated oil fatty acids: 45-70% Content of aromatic or cycloaliphatic !! Monocarboxylic acids: 0-20% Polyalcohol content: 15-25% Content of dicarboxylic acids: 0-16% Diisocyanate content 8-25% Amine number: 3-25 mg / KOH / g Acid number: below 5 mg KOH / g Hydroxyl number: 0-80 mg KOH / g Limiting viscosity number [;;]: 8-16 ml / g 6. Process according to claims 1 to 4, characterized in that before the emulsification with Water component (I) at 80 to 160 ° C, if necessary in the presence of a drying agent, for so long with air treated until a peroxide number of at least 20 garbage equivalents per kilogram and an increase in Limiting viscosity number (CHCIj, 20 ° C) by at least 1 ml / g is reached and / or the mixture of the compo- ?> elements (1) and (II) with 1.5 to 10 Mllllmol / 100g of the resin mixture of an aromatic and / or aliphatic Reacts diisocyanate in the presence of an inert solvent and optionally the solvent removed from the reaction mixture by distillation prior to neutralization and emulsification. 7. The method according to claim 6, characterized in that urethane modules are used as component (II) Alkyd resins are used, which have the following limit values: Unsaturated fatty acid content: 35-70% Content of aromatic or cycloaliphatic !! Monocarboxylic acids: 0-25 ¹ V Polyalcohol content 15-30% Content of dicarboxylic acids: 0-20% <ö Content of diisocyanates 8-25% M Amount: 3-25 mg / KOH / g | Acid number: below 5 mg KOH / g Hydroxyl number: 0-100 mg KOH / g § Limiting viscosity number [η \: 8-20 ml / g 8. The method according to response 6 and 7, characterized in that the reaction with the Dllsocyanat takes place with components which have a hydroxyl number! of 20 mg KOH / g or more. The invention relates to a process for the production of air-drying aqueous emulsions of urethane modules Alkyd resins and / or urethane oils. Here, polyethylene glycol (PEG) modlfizlerte are used as the emulsifying component vinylated and / or acrylated fatty acid esters are used. Acrylic-modified alkyd resins as binders for water-thinnable air-drying paints are described in US Pat 4133 786, and GB-PS 11 17 126 described. Likewise is the use of water-thinnable Urethane oils or urethane-modified alkyd resins for air-drying paints, e.g. B. from EU 00 17 199, EU 00 18665, DE-OS 1745 343, DE-PS 23 23546, US-PS 40 17514 and US-PS 40 17 514 and US-PS 4116902 is known. However, both groups of binders have specific disadvantages: The acrylic-modified alkyd resins show due to the reduced reactivity of the unsaturated fatty acids due to the copolymerization, it is only moderate Cross-linking and thus poor resistance of the paint films. They also require a high proportion of volatile substances toxic amines to neutralize the acid groups. The urethane oils and urethane-modified alkyd: o Resins cause major problems due to poor plgmenl wetting and poor compatibility with sikkatlven Problems with the paint production. In addition, it also applies to them that large amounts are used to stabilize the emulsions Amine quantities are necessary. It is also the combination of urethane oils or urethane-modified alkyd resins in emulsified form with polyvinyl or polyacrylic latices known (US-PS 39 19 145). Because of the inert, non-crosslinkable latex portion of these binders, only one can moderate film quality can be achieved, so that these products are only used for so-called "house palnts" will. It has now been found that air-drying aqueous emulsions of urethane-modified alkyd resins can be obtained and / or urethine oil is obtained if the emulsifying component used is PEG-containing polyol esters of unsaturated Fatty acids are used, these polyol esters being modified in specific catfish by graft polymerisation will. The inventive method for the preparation of air-drying aqueous emulsions of urethane-modified Alkyd resins and / ode. Urethane oils is characterized in that one