DD298418A5 - PIGMENTPRAEPARATIONEN - Google Patents

Abstract

Pigmented preparations containing A) an inorganic and / or organic pigment, B) a liquid oligourethane and optionally C) one or more additives customary for pigment preparations, the weight ratio being *, and the use of these preparations for pigmenting leather and synthetic leather dressing compositions.

Description

The invention relates to pigment preparations and their use for pigmenting leather and Kunstlederzurichtungmittel.

It is known to color water-insoluble leather and Kunstlederzurichtungungsmittel based on polyurethanes or water-insoluble cellulose esters with pigment preparations. In addition to pigment and conventional additives such as solvents, the pigment preparations used in this case usually also contain pigment binders based on collodion, cellulose acetate, cellulose acetobutyrate, ethylcellulose or polyvinyl chloride-polyvinyl acetate copolymers, optionally with addition of plasticizers or of plasticizers alone, such as dibutyl phthalate. These pigment preparations often have an unfavorable effect on the properties of the finishing agents for leather and luster imitations and on the finished article. On the one hand, they harden the leather or the imitation leather, they reduce the wet and dry kinks and worsen the cold resistance, on the other hand they can sweat out. Above all, the light fastness and the yellowing under the influence of heat or the adhesion are adversely affected by the known forming agent.

These disadvantages are attempted to be avoided by using as binders for pigments the same odor-like polyurethanes as are also used as binders in leather finishing or in the coating of synthetic leather. Thus, the identified disadvantages can be partially resolved; however, it is necessary to apply a finely-tuned pigment preparation to each dressing, e.g. Polyurethanes with each other and polyurethanes with collodion and other cellulose derivatives are only very partially compatible.

There was therefore a need for pigment preparations which can be used universally for all leather and synthetic leather dressing compositions and, moreover, do not have the disadvantages of known pigment preparations. Of particular advantage are preparations in which the binder is copolymerized or added to the coating or coating composition.

The invention relates to pigment preparations containing A) an inorganic and / or organic pigment, B) a liquid oligourethane and optionally C) one or more additives customary for pigment preparations, the weight ratio A): B) = 1: 0.1-50.

Preferably, the pigment is dispersed in the oligourethane.

Preference is given to preparations which contain A) 2-60% by weight, more preferably 5-30% by weight, organic pigment or 2-80% by weight, especially 10-65% by weight, inorganic pigment, B) 5-98% by weight. % Oligourethane and C / 5-90% by weight, particularly preferably 8-30% by weight additive, in particular solvent, wherein A) + B) + C) = 100% by weight.

Preferred oligourethanes have sterically hindered or blocked isocyanate groups. Very particular preference is given to those oligourethanes which are capable of reacting with the other polymers present under conditions of use.

The pigment preparations may optionally contain conventional additives, such as solvents, adjusters or thickeners.

Suitable solvents are alcohols such as isobutanol, cyclohexanol, tert-butanol, iacetonoyl alcohol, ethyl glycol, glycol monomethyl ether, ketones such as methyl ethyl ketone, cyclohexanone, esters such as butyl acetate, phthalic acid esters such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, phosphoric acid esters such as tricresyl phosphate, adipic acid esters such as dibutyl adipate, alkyl sulfonic acid esters such as pentadecane sulfonic acid phenyl or tolyl ester, d. H. Products

as she ζ. B. for softening nitrocellulose or PVC are commonly known, or methoxy or ethoxypropyl acetate or acid amides such as dimethylformamide or methylpyrrolidone and proportionate hydrocarbons such as benzene, toluene or

Xylene. Preference is given to cyclohexanone, dimethylformamide or methoxypropyl acetate. Particular preference is given to using solvents which have a boiling point> 120 ^° C. Preference is given to using OH- or NH-group-free solvents. In a particular embodiment, such

"Release emitter related, as they are z. B. are common for softening of PVC; d. H. Solvents that can remain in the substrate and do not need to be evaporated.

The pigment preparations can be easily prepared by dispersing the components in a conventional manner Wet crusher, such as a rotor stator mill, a bead mill or a ball mill manufacture. The Particle size of the dispersed pigments should be 0.2 to 2 mm. The pigments used in the inventive Pigment preparations are incorporated, are not subject to any restriction, they may be organic or inorganic nature

his. Suitable organic pigments are, for. B. those of the azo, anthraquinone, azoporphine, trioindigo, dioxazine,

Naphthalenetetracarboxylic or perylenetetracarboxylic acid series and laked dyes such as Ca, Mg or Al lacquers of Sulfonic acid and / or carboxylic acid groups containing dyes, of which a large number, for example Color Index, 2nd edition, are known. Suitable inorganic pigments are, for. As zinc sulfides, cadmium sulfides or selenides. Ultramarine, titanium dioxides, iron oxides, nickel or chromium compounds and carbon black. Suitable oligourethanes are those having molecular weights of 5,000 to 50,000. Preferred are those of a molecular weight of

10,000 to 50,000 and more preferably from 15,000 to 40,000. Very particular preference is given to using oligourethanes which do not yellow or degrade under the influence of oxygen, light, heat or water.

To prepare the oligourethanes, it is possible to use all customary polyesters, polyethers, polycarbonates, polyetheresters, isocyanates and polyesters Chain extenders are used on glycol and / or amine-based. Preferably, polyesters of adipic, succinic, glutaric, carbonic, phthalic, terephthalic, isophthalic, (mono-, di-, tri-)

and poly) ethylene or propylene glycol, butanediol, hexanediol, polycaprolactone, mixtures of the acids or glycols in tandem, as well as amino-containing polyols. Voi preferably find esters of adipic, phthalic and

Carbonic acid use. Polyethers based on ethylene glycol, propylene glycol, butanediol (which are also present in a mixture

can), which may be started by known methods on optionally aminiei ton alcohols, can be used alone or together with the esters.

In principle, all polyisocyanates are suitable for the preparation of the oligourethanes. Preference is given to polyisocyanates such as

optionally polymerized toluylene or methylene diphenyl diisocyanate or hexane or isophorone diisocyanates. Because of their high lightfastness, the aliphatic isocyanates are very particularly preferred. The resulting

Oligourethanes may be OH-terminal, isocyanate-terminal or blocked. The oligourethanes preferably contain sterically hindered free or blocked isocyanate groups. The oligourethanes used according to the invention have preferably been prepared in an NCO: OH ratio> 1. As blocking agents are, for example, primary, secondary or tertiary alcohols or oximes, z. B. butanone oxime, called. The blocked isocyanate groups are used under the conditions under which the pigment preparations are used,

released and then able, e.g. to react with coating compositions, coatings or Lederzurichtungsmitteln and thereby improve their properties.

Organic leather finishing agents that can be colored with the pigment preparations of the present invention are

for example described in DE-A1174937 and 1278064. Almost all binders dissolved in organic solvents can be pigmented with the pigment preparations according to the invention. They are particularly suitable for the

Pigmentation of aromatic and aliphatic polyurethane one-component and also amine-containing Two-component systems and for lacquers based on cellulose derivatives, such as those for the finishing of leather or leather Leather substitutes are used. The selection of the pigment preparations is made according to the desired color effect. If high opacity is desired, preparations of inorganic pigments are used. Should the treated substrate

In contrast, show a translucent hue with high brilliance, are used preparations with organic pigments.

In addition, one takes into account the given by the pigment fastness properties, such as light and migration fastness, heat resistance In particular, these novel pigments are suitable for use in reactive polyurethane systems as described, for. In 2- Component method according to DE-A 3309992 or in "high-solid systems" (according to DE-A 3239900) find application. Specifically, the embodiment in which oligomers with sterically hindered or blocked isocyanates as Forming agent find use is suitable for this application. In this case, the forming agent reacts under the Application conditions with the reactive coating products. As a result, the forming agent is firmly in the Coating with built-in. The erfindungsmäßen pigment preparations have over known the advantage that they are very easy to produce

are universally applicable and not adversely affect the properties of the dressing to be pigmented and the substrates and in particular do not deteriorate the specified by the pigments fastness. Particularly preferred oligourethane, the softening points between -40 ° C and +25 ⁰ C possess. After evaporation of the optionally present solvents in drying channels, they usually do not form closed films at room temperature from their solutions in organic solvents. Surprisingly, they do not result in dressings having a sticky feel and poor hot friction strength. Also, the dressing has a good cold resistance and a good wet and

Dry kinking resistance. On the other hand, they also do not migrate out of the coating or dressing system. The addition of Plasticizers instead of solvents of the type adipic acid or phthalic acid ester counteract hardening; if

these products are used in amounts below 30%, preferably below 10%, based on the coating agent, these compounds do not migrate.

When using mixtures of different pigments, it comes in pigment preparations with binders Cellulose base or polyvinyl acetate often to float, especially the organic pigments. By the

Pigment preparations according to the invention this is prevented and optimally improved the compatibility with a variety of coating compositions, so that they are universally used for the dyeing of binders, eg. B. can also be used for textile printing, üie following examples are intended to illustrate the invention.

1. Preparation of olligourethanes

Example 1.1

In this example, an oligourethane with blocked isocyanate groups is described:

1600g of a hexane diol neopentyl glycol adipate of OH number 63 to 70 (2000mmol OH), after thorough dehydration in vacuo in a 4L beaker with 444g (4000mmol NCO) isophorone diisocyanate and 80g (200mmol NCO) of a triisocyanatohexyl biuret (ie 360 minutes) at 90 to 100 ° C until the theoretical NCO value is reached and then treated with a further 240g (2760mmol) butanone oxime and reacted for another 200 minutes at 90 to 100 ° C with stirring. The mixture is then adjusted to 70% concentration with di-n-butyl phthalate. The result is an oligourethane with 2.80% blocked! Socyanatgruppen having at 25 ° C has a viscosity of 22000mPas.

Example 1.2

1600g of a hexane diol neopentyl glycol adipate of OH number 63 to 70 (2000mmol OH), after thorough dehydration in vacuo in a 4L beaker with 444g (4000mmol NCO) isophorone diisocyanate and 80g (200mmol NCO) of a triisocyanatohexyl biuret (ie 360 minutes) at 90 ° to 100 ° C. until the theoretical NCO value has been reached and then a further 240 g (2760 mmol) of butanone oxime are added and stirring is continued for a further 200 minutes at 90 ° to 100 ° C. The reaction is then carried out with methoxy type, opylacotate set to 70% concentration. the result is an oligourethane with 2.80% blocked isocyanate groups, having a viscosity of 2300mPas at 25 ⁰ C.

Example 1.3

2000g of a polypropylene glycol ether of OH number 56 (2000mmol OH) are after thorough dehydration in vacuo in a 4-liter stirred beaker with 354g (4200mmol NCO) hexamethylene diisocyanate while (ie, about 300 minutes) reacted at 90 to 100X with stirring until the theoretical NCO value is reached and then treated with a further 240g (2760mmol) butanone oxime and reacted for another 200 minutes at 90 to 100 ⁰ C with stirring. Subsequently, it is set to 70% concentration with Mothoxypropylacetat. The result is an oligourethane with 2.70% blocked isocyanate groups, which has a viscosity of 200mPas at 25 ° C.

Example 1.4

2000g of a Hexandiolpolycarbonats the OH number 56 (2000mmol OH) are after thorough dehydration in vacuo in a 4-liter beaker with 444g (4000mmol NCO) isophorone diisocyanate and 80g (200mmol NCO) of a Triisocyanatoxhexvlbiurets as long (ie about 360minutes) at 90 to 100 ° C reacted until the theoretical NCO value of 2.17% is set.

Subsequently, with methoxypropyl acetate to 70% concentration. The result is a urethane with isocyanate groups, which has a viscosity of 1300 mPas at 25 ⁰ C.

Example 1.5

2000 g of a polypropylene glycol ether of OH number 56 (2000 mmol OH), after thorough dehydration in vacuo in a 4 L stirred beaker with 183 g (2100 mmol NCO) of 2,4 / 2,6-diisocylindnato-1-methylbenzene and 176 g (2100 mmol NCO) of hexamethylene diisocyanate as long (ie, about 200 minutes) at 90 to 100 ⁰ C reacted until the theoretical NCO value is reached and then treated with a further 240g (2760 mmol) butanone oxime and reacted for a further 120 minutes at 90 to 100 ⁰ C with stirring. Subsequently, with methoxypropyl acetate to 70% concentration. Ks formed an oligourethane with 2.68% blocked isocyanate groups, which has a viscosity of 300mPas at 25 ⁰ C.

Example 1.6

1600g of a hexane-1-ol neopentyl glycol adipate of OH number 63-70 (2000mmol OH), after thorough dehydration in vacuo in a 4L stirred beaker with 610g (4200mmol NCO) of 1,3,5-triisopropylbenzene-2,4-diisocyanate (sterically hindered) as long (ie, about 300 minutes) at 90 to 100 ⁰ C reacted until the theoretical NCO value is reached and then treated with a further 240g (2760mmol) butanone oxime and another 200 minutes at 90 to 100 ⁰ C with stirring implemented. Subsequently, with methoxypropyl acetate to 70% concentration. The result is an oligourethane with 2.60% blocked isocyanate groups, which has a viscosity of 3800 mPas at 25 ⁰ C.

2. Preparation of the Plgment Preparations

Example 2.1

1.8 kg of pigment binder from Example 1.1 are diluted with 1.7 kg of di-n-butyl phthalate, 6.5 kg of titanium dioxide pigment ('Bayertitan RFK-2) and stirred for 15 minutes by means of a dissolver at 2000 U / min. After milling on the bead mill, a well-dispersed pigment paste is obtained.

Example 2.2

1.8 kg of pigment binder from Example 1.2 are diluted with 85 g of methoxypropyl acetate and 85 g of trimethylbenzene mixture ("Solvsso 100, ESSO), 6.5 kg of titanium dioxide pigment (* Bayertitan RFDI) and stirred for 15 minutes by means of a dissolver at 2000 U per min. After milling on the bead mill, a well-dispersed pigment paste is obtained.

Example 2.3

2.0 kg of pigment binder from Example 1.3 are diluted with 6.99 kg of methoxypropyl acetate and 10 g of triethanolamine, then 1.0 kg of carbon black "Monarch 800 (from Cabot) is introduced and stirred for 20 minutes by means of a dissolver at 2000 rpm. Subsequently, the carbon black dispersion is ground once or twice on a bead mill with glass beads of 1 mm diameter until the required black depth and coverage are obtained with cooling.

Example 2.4

1.95 kg of pigment binder from Example 1.6 are diluted with 1.3 kg of methoxypropyl acetate and 1.2 kg of Solvesso 100 (from ESSO), 5.5 kg of iron oxide brown pigment, type 645 T (from BAYER AG) are introduced and treated by means of a dissolver for 15 minutes at 2000 rpm.

touched. Subsequently, the dark brown pigment dispersion is ground once or twice on a bead mill with glass beads of 1 mm diameter until the required color intensity and coverage are obtained, with cooling.

In order to obtain color pastes of the same viscosity with other inorganic pigments, it is necessary to match the quantitative ratio of pigment: binder and solvent to the particular pigment.

Example 2.5

2.6 kg of pigment binder from example 1.5 are diluted with 5.7 kg of methoxypropyl acetate, 1.7 kg of ®Novopermrot F5RK (from HOECHSTAG) are introduced and the mixture is stirred for 20 minutes using a dissolver at 2000 rpm. touched. Subsequently, the pigment dispersion is ground once or twice on a bead mill with glass beads of 1 mm diameter to obtain the required color strength and brilliance with cooling.

Example 2.6

2.2 kg of pigment binder from Example 1.4 are diluted with 6.0 kg methoxypropyl acetate, 1, Pkg ®Paliogenrotviolett K 4985 (BASF) registered and stirred for 20 minutes by means of dissolver at 2000 rev / min. Subsequently, the pigment dispersion is ground once or twice on a bead mill with glass beads of 1 mm diameter until the required color intensity and brilliance are achieved, with cooling.

Equally good pigment preparations are obtained when using instead of ®Novopermrot F5RK and ®Paliogenrotviolett K 4985 other organic pigments. In order to obtain color pastes of the same consistency, it is necessary - as described for the inorganic pigments in Examples 2.1.2.2.2.4 - to match the quantitative ratio of pigment: binder and solvent to the particular organic pigment.

For the pigmentation of acetobutyrate paints (see application in example 3.1) or of collodion paints (see application in examples 3.2 and 3.3) or of polyurethane solutions (see application in examples 3.4-3.14), these pigment preparations are used either alone or in combination with the titanium dioxide pigment preparations described in Examples 2.1 and 2.2 or with the carbon black pigment preparation (Example 2.3) or with the inorganic pigment preparations from Example 2.4.

All color pastes are well miscible with each other without Flokkulations- and Ausschwimmerscheinungen; As a result, deposits, streaks of color or hue fluctuations in reverse coating do not occur. The nuances set with the pigment preparations are easily reproducible at all times.

3. Pigmentations

Example 3.1

To a solution of 25g cellulose acetobutyrate (butyryl content 49%, viscosity 20% in acetone at 20 ° C about 20Pas), 5g di-n-butyl phthalate, 4g n-butyl stearate, 2g of a polyether siloxanes (prepared according to DE-OS 3244955 Example 1 A), 104 g of 2-ethylhexyl acetate, 410 g of methoxypropanol and 410 g of n-butyl acetate, 40 g of the titanium dioxide preparation from Example 2.1 are added. After a stirring time of 5 minutes, a ready-to-use white paint is obtained, which is very easy to spray and extremely strong. It is lightfast, amine-resistant and resistant to yellowing up to 17O ⁰ C. The varnish is particularly suitable as a strongly opaque white final finish on polished and full-grain leathers.

Example 3.2

To a solution consisting of 32 g of an ester-soluble collodion wool (butanol wet, 65%, standard type 9E), 40 g of di-n-butyl phthalate, 15 g of castor oil, 50 g of 2-ethyl-n-hexyl acetate and 813 g of vinyl lace tat While stirring, 50 g of the carbon black preparation from Example 2.3 are added. After a stirring time of 5 minutes to obtain an intensely black colored collodion paint, which is sprayed with an air-spray gun, is particularly suitable as a high-gloss final finish on ground and full-grain leathers.

Example 3.3

To a solution consisting of 53 g of an ester-soluble collodion wool (butanol wet, 65%, standard 15 E), 24 g of di-n-butyl phthalate, 4 g of castor oil, 8 g of butyl stearate, 110 g of 2-ethyl-n-hexyl-acetate, 12 g of benzyl alcohol, 185 g of n-butyl acetate, 2 g of triethanolamine, 15 g of di-n-octylsodium sulfosuccinate, 12 g of an adduct of about 20 moles of ethylene oxide to 1 mole of nonylphenol, 50 g of the carbon black formulation from Example 2.3 are added with stirring. After good distribution of the pigment dispersion is emulsified with 525 g of water.

The resulting water-reducible black emulsion is very well suited as a deep black finishing agent for thermoplastically dressed, ground and full grain leather.

Example 3.4

To a solution of 80 g of a polyurethane resin (prepared according to DE-OS 2423764), 130g tert. Butanol, 100 g of toluene, 250 g of trimethylbenzene mixture ("Solvesso 100, ESSO company), 27 g Celluloseacetobutyrat (butyryl 49%, 20% viscosity in acetone at 20 ° C about 20Pas), 3g polyethersiloxane (prepared according to DE-OS 3244955 Example 2 A), 100 g of methyl ethyl ketone, 260 g of methoxypropanol, 50 g of the iron oxide preparation from Example 2.4 are stirred. The finished paint is sprayed with an airless spray gun and has a s ^r .nr good flow and results after application to leather or imitation leather a shiny, highly elastic brown finish, which is particularly suitable as a covering final finish for furniture leather.

Example 3.5

From the pigment preparation according to Example 2.2, a pigmented polyurethane solution used for textile coating can be prepared as follows:

To a solution consisting of 25 g of a polyurethane, 45 ml of dimethylformamide and 30 ml of methyl ethyl ketone, with stirring with a high speed stirrer at a speed of 200 to 300U / min. 8g of the titanium dioxide pigment preparation according to Example 2.2 given. After a stirring time of 3 to 5 minutes to obtain a finely divided, stable pigment dispersion, which is very well suited for textile coating by the inversion process. The polyurethane films produced therewith by known methods on textiles are dyed uniformly and without specks. The one-component polyurethane used is prepared from a polyester of adipic acid and hexanediol / neopentyl glycol having an average molecular weight of 500 to 3000 and diphenylmethane-4,4'-diisocyanate and subsequent reaction with butanediol.

Example 3.6

To a solution consisting of 30 g of a nebulizable OH-terminated polyurethane and 70 g of ethyl acetate, after addition of 5 g of methyl ethyl ketone with stirring with a high speed stirrer at a speed of 200 to 300U / min. 8g of the titanium dioxide Pigmentzubsreitung na h Example 2.2 given. After a stirring time of 3 to 5 minutes, a finely divided, stable pigment dispersion is obtained which, after addition of a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate and a heavy metal salt as accelerator, for the coating of textiles after the reverse or Direct method is suitable. The polyurethane films thus produced by known methods are dyed uniformly and without specks.

Example 3.7

100 g of a 30% aliphatic polycarbonate-polyurethaneurea, prepared according to British Pat. No. 1,418,550, are mixed with 15 g of a pigment preparation according to the invention from Example 2.5 on a mechanical stirrer and applied to an embossed silicone release paper by means of a stationary doctor blade or similar known coating apparatus. Edition 30 g / m ² solid substance.

After passing through a heated to 80 to 125 ⁰ C drying channel and cooling the opacity is compared with an analogously prepared other pigment preparation. The pigment preparation according to the invention has an improved covering power.

Example 3.8

The top coat described in section 3.7 is not sufficient, therefore another aromatic PUR must be painted in DMFiMEK 50:50 with a viscosity of 25,000 mPas / 25 ° C. Edition 50 g / m ² fixed. The PUR is prepared from 2,000 g of a polypropylene glycol ether of molecular weight 2000,200g butanediol-1,4 and 800g 4,4'-diphenylmethane diisocyanate.

For coloring, 20 g of the pigment preparation according to the invention from example 2.5 are thoroughly mixed in.

Example 3.9

1000g of a blocked isocyanate prepolymer according to DE-OS 2,902,090 Example 1 are prepared with 100 g of pigment paste from Example 2.3,90g S.S'-DimethyM ^ '- diaminodicyclohexylmethane mixed under vacuum and simultaneous heating up to 4O ⁰ C. Edition 200g / m ² fixed; Crosslinking temperature 150 to 16O ⁰ C. As adhesive line is the above-described blocked NCO prepolymer with the addition of diamine. 50 g of pigment preparation from Example 2.3 and 200 g of a 40% PUR dispersion and 30 g of a water-soluble silicone oil are intimately mixed with the aid of a dispersing agent. This paste, which can be stored at room temperature for an extended period of time, is applied once directly to an embossed release paper, at another time onto a silicone matrix and also onto an endless steel strip; All of these temporary substrates may already have one or more layers consisting of the precoated products or other chemicals (acylates, for example). The products are applied by means of a known coating unit (squeegee, spray gun, pressure roller, etc.), immediately thereafter endless material such as woven fabric, knitted fabrics, nonwovens and coagulated fabrics is laminated over rolls. By rolling from different materials (metal, rubber or hard paper or foam) consisting, passed and in a hot on 130 to 17O ⁰ C, heated by convection heated drying duct out

 At the end of the dryer is cooled by rollers and removed from the separator, which can be reused.

Example 3.10

The pigment preparations listed in Examples 2.1 to 2.6 are very suitable for the pigmentation of a two-component polyurethane for the coating of leather by the inversion process. This is done as follows:

200 g of p-toluenediamine are golöst in 800 g of methyl ethyl ketone with stirring over 5 minutes. 200g of pigment preparation 2.4 are added to the yellowish brown solution. Although this pigment dispersion is water-thin, it has a storage stability of several weeks and, after conversion with a polyisocyanate, is very well suited for inversion leather coating. The polyurethane films thus produced by known methods are dyed uniformly and without specks. The polyisocyanate used is prepared by reacting p-tolylene diisocyanate with a polyester of adipic acid, terephthalic acid and diethylene glycol having an average molecular weight of 1,000 to 3,000.

Example 3.11

On a Beschichtungsungsanla _d e by means of a two-component Misu ,, .stole as z. As described in US 4310493, 342g (262mmol NCO) of the prepolymer A (see below) processed with 425g (250mmol) diamine hardener solution. The hardener solution v / ar is composed as follows:

147 parts of 1,1-bis (4-amino-3-methylphenyl) cyclohexane

139TeIIe 3-methyl-2,4-diaminobenzoic acid (2-ethylhexyl) ester

2,800 parts of ethyl acetate

150 parts of a formed iron oxide pigment according to example 2.4

150g of a polyetherpolysiloxane of the idealized formula.

_x 0 - [(CH ₃ ) ₂ SiO ₃ -Si (CH ₃ ) ₂ -CH ₂ -O- (RO) _m -C ₄ H ₉

CH ₃ -Si-O - [(CH ₃ J ₂ SiO) ₅ -S 1 (CH ₂ ) ₂ -CH ₂ -O- (RO) _1n -C ₄ H ₉

^ O- [(CH ₃ ) ₂ SiO] ₅ -Si (CH ₃ ) ₂ -CH ₂ -O- (RO) _1n -C ₄ H ₉

in which

m is an integer between 27 and 35 and R is ethylene and propylene radicals.

Split leather, textile fabrics, nonwovens and nonwoven are coated according to the inversion process by means of a PUR pistol spraying machine, as described, for example, in US Pat. As described in US 4310493 ι is. The pistol spraying machine points; as a main component a heatable reservoir for the prepolymer, a reservoir for the curing agent preparation, each a metering device for the curing agent and the prepolymer and for mixing and atomizing the components of a two-component PU spray gun as in US 4310493, a heatable feed for the prepolymer, a Supply for the hardener, a line for solvents and a supply for compressed air.

The prepolymer is added to the heatable storage tank and heated to 50 ° C to 8O ⁰ C in order to lower its viscosity. The hardener preparation is placed in the container intended for it. Separate lines with intermediate metering devices are used to transport prepolymer and hardener preparation into the gun. The quantities conveyed are in the ratio of the equivalent weights of NCO: NH ₂ in the amounts of 1.00: 1 to 1.75: 1. The mass flow rate is variable and depends on the desired layer thickness and depending on the area which is coated in the unit time, and the constituents of the reaction mixture are in the mixing chamber and in the mixing tube of the Zwelkomponenten PU spray gun - as described in detail in US 4310493 - Intensively mixed in a short time and pressed by compressed air through the outlet nozzle. The reaction of the components begins immediately, ie already during the mixing process.

At the outlet of the gun, the mixture is additionally mixed by Luftwirbei generated with compressed air (operating pressure 3 to 6kg / cm ² ) and converted the cone shape of the Spritzsirahles into a broad jet. The gun changes to a width of 150 cm about 25 to 35 times per minute over a silicone rubber coated die (which has the imprint of natural leather) or another release liner over it The release liner is moved at a speed of 2 to 10 meters / minute The mass sprayed on the die or the release carrier runs like a film, the viscosity of the mixture increases, and after about '-'Q to 90 seconds, calculated from the time of spraying, a pasty state is reached In the reacting mass to be coated split leather or other substrates is placed and pressed.

The entire coating then passes through a heated to 60 to 120 ⁰ C drying channel. After about 3 to 6 minutes, calculated from the time of spraying, the coating is peel-free from the die or separator carrier.

The »polyurethaneurea layer has a thickness of 0.15 to 0.45 mm.

The coated surface material has a natural leather deceptively similar grain, is dry after a short time, stackable and z. B. processable on popular shoe machines. The adhesion between coating and split leather is excellent, the handle pleasantly dry, soft.

Example 3.12

474 g (400 mmol NCO) of the prepolymer B (see below) are processed with 130 g of the hardener solution described below on a coating system analogous to Example 3.11.

400 g 2,4-toluenediamine

600 g of methyl ethyl ketone.

400 g of the pigment suspension 2.5 described according to the invention

100 g of the course according to Example 3.11

Surprisingly, it has been found that this suspension of various products does not have to be held in suspension with a mechanical stirrer over a relatively long period of time. Normally, pigment dispersions tend to sediment under these conditions, which is not the case with the dispersions of the invention. The pigment formation according to the invention is more advantageous because no air bubbles are stirred in by the required mechanical stirring; So they are missing in the hardened film. The coatings on surface carriers produced from the prepolymer and the non-mechanically stirred hardener solution are characterized by compact films, ie. H. film values disturbed by less air inclusions.

The resulting films or coatings had the following properties in comparison to a container equipped with a mechanical stirrer:

Container with Without container agitator agitator tensile strenght 10MPa 12MPa Rruchdehnung 440% 500% Tear strength 22daN 24daN

Example 3.13

640 g (888 mmol) of the prepolymer C (εϊΛΐιβ below) are intimately mixed with 582 g of a curing agent and poured onto a release liner.

The hardener preparation corresponds to the following composition:

120 g of pigment preparation from Example 2.5

600 g of a mixture of 170 g of S ^^ - trimethyl-δ-amino-methyl-cyclohexylamine (IPDA) 13 g of water and 417 g of methyl ethyl ketone are refluxed for 2 hours. After cooling, the mixture is ready for use as a hardener.

Of the 170g (1 mole) of IPDA employed, the mixture is:

a) 12.9 mol% as free IPDA

b) 41.6 mol% as

^C 2 ^H

^2H 5

c) 45.5 mol% as bis-methyl ethyl ketone ketimine of IPDA.

(The composition was calculated from the gas chromatographic analysis of the mixture.) In addition, the mixture still contains a total of 37.9 g of water, which are calculated from the sum of the water of reaction and the additional amount of 13 g used. (The theoretically required amount of water for the hydrolytic decomposition of the ketimine groups to amino groups is 24.9 g.) The NH ₂ equivalent of the hardener mixture is 600 g.

Example 3.14

The Rußzuboreitung from Example 2.3 is very well suited for the pigmentation of a two-component polyurethane for the painting of leather by the cold paint process:

To a solution consisting of 70g of a crosslinkable, low-branching OH-terminated polyester, 30 g of ethyl acetate, 20 g of butyl acetate, 20 g of cyclohexanone and 10 g of methylglycol acetate are added with stirring at a speed of 200 to 300 rpm with a high speed stirrer. 15 g of the carbon black preparation given. After a stirring time of 5 minutes, a finely divided, stable pigment dispersion is prepared which, after addition of 41 g of a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate and a heavy metal salt as accelerator, is suitable for the coating of leather by the cold paint process is. The patent leather thus produced by known methods are dyed uniformly speckle-free. The black tone is flowery and brilliant. The polyester used is prepared from adipic acid, diethylene glycol and trimethylolpropane and has an average molecular weight of 1000 to 3000.

Example 3.15

A pigment preparation prepared according to DE-A 2801817, Example 1, page 7 to 8, line 3, is best suited for use alone. However, it has been found that mixtures of organic and inorganic pigments, all prepared in the same pigment binder, do not remain uniformly mixed without constant mechanical stirring. Especially after prolonged standing of the ready-to-use solutions, settling of the specifically heavier inorganic pigments and floating of the specifically lighter organic pigments can be observed.

Example 3.16

Pigment preparations of collodion-containing finished preparations are only conditionally suitable for use on flexible substrates, such as leather, textiles, textiles and the like.

Pigment preparations with collodion as the forming agent, optionally with the addition of plasticizers, affect the properties of the elastic dressing, e.g. PU-based, unfavorable for leather and imitation leather. After prolonged storage, they harden the leather or imitation leather, worsen the handle and the grain, reduce the kink resistance and worsen the cold resistance. Above all, the lightfastness and the yellowing under the influence of heat and amine and the adhesion are negatively influenced by these pigment preparations.

4. Preparation of the NCO Prepolymers for Examples 3.11 to 3.13

PrepolymerA

60 parts of a polyester of adipic acid, hexanediol and neopentyl glycol having an OH number of 64 (73.5 equivalents OH) are dehydrated for 1 hour in an autoclave at 11O ⁰ C and at 110 ⁰ C in the presence of 18.2 parts of toluene with 12 , 8 parts of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer, 147 equivalents) to a prepolymer having an NCO content of 3.2%. Viscosity at 2O ⁰ C 4000mPas and at 7O ⁰ C 500mPas.

prepolymers

500 g of a polyester of adipic acid and ethylene glycol (0.53 mol) are dehydrated at 13 torr and 110 ° C for 1 hour. The polyester is then reacted at 110 ° C for 60 minutes with 132.5 g of 4,4'-diisocyanatodiphenylmethane (1.06 moles NCO). This gives a prepolymer with ei.iem NCO content of 3.54%.

Prepolymer C

100 g of a linear polyether of 50% by weight of ethylene oxide and 50% by weight of propylene oxide (started on 1,2-propylene glycol) with the OH number 56 and 1000 g of a trifunctional polyether of 27.5% by weight of propylene oxide and 72.5% by weight. % Ethylene oxide (started from glycerol) with the OH number 36, after dehydration with 666g 4,4'-diphenylmethane diisocyanate at 90 ° C implemented. Reaction time 45 minutes. NCO content 5.8%, equivalent weight 724g.

Claims (10)

1. Pigment preparation ^ containing A) an inorganic and / or organic pigment, B) a liquid oligourethane and optionally C) one or more additives customary for pigment preparations, the weight ratio A): B) = 1: 0.1- 50 is. 2. Pigment preparations according to claim "!, Containing A) 2-60Gew .-% organic pigment, B) 5-98Gew .-% oligourethane and C) 5-90 wt .-% additive, in particular solvent, wherein A) + B) + C) = 100% by weight. 3. Pigment preparations according to claim!, Containing A) 5-30% by weight of organic pigment, B) 5-98% by weight of oligourethane and C) 8-90% by weight of additive, in particular solvent, where A) + B) + C ) - 100% by weight. 4. Pigment preparations according to claim 1 comprising A) 2-80% by weight of inorganic pigment, B) 5-98% by weight of oligourethane and C) 5-90% by weight of additive, in particular solvent, where A) + B) + C) = 100% by weight. 5. Pigment preparations according to claim 1, comprising A) 10-65% by weight of inorganic pigment, B) 5-98% by weight of oligourethane and C) 8-90% by weight of additive, in particular solvent, where A) + B) + C) = 100% by weight. 6. Pigment preparations according to one or more of claims 1-5, characterized in that the molecular weight of the oligourethane is 5000-50000. 7. Pigment preparations according to one or more of claims 1-5, characterized in that the molecular weight of the oligourethane 15,000-40000. 8. Pigment preparations according to one or more of claims 1-7, characterized in that the oligourethane has sterically hindered isocyanate groups. 9. Pigment preparations according to one or more of claims 1-8, characterized in that the oligourethane has blocked isocyanate groups. 10. Use of the pigment preparations according to one or more of claims 1 to 9 for pigmenting leather and artificial leather dressing compositions.