DE2407568A1 - PIGMENT PASTE - Google Patents

Description

Bayer Aktiengesellschaft

Zontral area patents, trademarks and licenses

509 Leverkusen, Bayerwerk

Jo / Bre

\ Feb. 5, 197

Pigment pastes

Homogeneous or cellular polyurethanes are available in many variations in use »Most systems are also colored or pigmented. The dyes or pigments are used for coloring usually as a dye or pigment paste shortly before processing the reactive system, which consists of a One-component system with reactive NCO groups or from a two-component system with polyol and polyisocyanate components can exist, admittedly. For example, German Patent 1,028,771 describes pigment pastes which ε-ls pigment carrier high-boiling organic liquids from the class of plasticizers known in the paint and plastics industry. There are also pigment pastes known that contain either a hydroxyl-containing polyester or polyether. Especially when it comes to polyurethane foam production However, it turns out that there is a greater or lesser incompatibility between polyester polyols and polyether polyols exists, which makes it necessary to use different pigment pastes for ether and ester foams.

Pigment binders with both polyester polyols and polyether polyols as well as one-component polyurethane systems are compatible, have not yet become known. The pigment pastes made with them should continue to be a have good stability and flowability.

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We have now found that low molecular weight reaction products of aromatic diisocyanates with polyols and monoalcohols have the broad compatibility that is sought and are suitable for supplying stable, flowable concentrated pastes with pigments. It is of particular advantage that the resins soluble in alcohols, esters, ketones and aromatic hydrocarbons exhibit particularly good pigment wetting. These resins can be produced by methods known per se. Products with the desired properties are obtained in particular with toluene-2,4, 2,6-toluene diisocyanate or the technical mixtures also acar with mixtures of Toluylondiioocyarx-t and other diisocyanates such as: \ ^T aphthylen-l, 5- diisocyanate ο ei er Diphenyimethen- ¹ ] -, '+ ¹ -diioccyanat. Suitable polyols are diols with 2-10, especially 5-δ carbon atoms, but also triolo vrie trimethylolpropane and their mixtures with one another, al :; r ,. . ' Alcohols, aliphatic and cycloaliphatic products with 6-3 carbon atoms, possibly mixed with shorter or longer-chain alcohols or glycol monoethers. However, products such as benzyl alcohol or phenoxyethanol can also be used as monoalcohols. Resins are obtained having a melting range of 80 to 120 ⁰ C, the solutions in 40 6ige Glkyolmonomethylätheracetat at 25 ° C a viscosity of 10 - 120 centipoise, preferably from 15 to 60 centipoise (measured according to Höppler falling sphere viscometer).

The pigment preparations contain 5 - 80 % pigment, 6 - 50 % of the low molecular weight urethane resins and 20 - 90 % of a solvent or diluent which can be free or containing hydroxyl groups. Thickeners such as highly disperse silica, special montmorillonites, which can also contain organic ammonium bases, and fillers such as kaolin, talc or blanc fixe can also be added to the solvent-containing pigment pastes.

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The solvents and diluents can be used according to solubility the polyester, polyether or NCO group-containing solvent-free or solvent-containing one-component systems to be colored to be selected. In addition, the selection is also based on the properties of the pigment to be incorporated, which is special can have an influence on the flowability and stability of the pigment preparation.

In addition to the known hydroxyl group-free solvents, the hydroxyl group-free alkyl and / or aryl esters of di- or polybasic acids such as adipic acid, phthalic acid or phosphoric acid used as plasticizers, but also esters of aromatic or aliphatic monocarboxylic acids with polyols such as glycerol triacetate are available. Suitable hydroxyl-solvents are for example esters, ketones and aromatic hydrocarbons with boiling points up to 180 ⁰ C. However, a special possibility is also to solve the low molecular weight urethane in hydroxyl-containing esters or ethers which are reactive with isocyanate. When urethane is formed, these solvents are completely incorporated. For example it is possible to solve these resins in monoethers of di- or Triäthylenglkyols "or short chain Äthylenoxidderivaten of phenol or its substitution products or at temperatures of about 100 ⁰ C, a resolution of the urethane in a linear polyether of propanediol and propylene oxide with an average molecular weight of 2000. Such crosslinkable products are preferred, for example in foam molding, where the NCO consumption of the pigment paste can be taken into account with a fixed recipe and the mechanical properties of the end product must be optimal.

The pigment pastes can be produced in conventional wet grinding units, for example in kneaders, attritors, Roller mills and with particular advantage in tendons Agitator mills with peripheral speeds of 5-60 m / sec,

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preferably 10-20 m / sec, the grinding media in the size of et v / a 0.1-10 IHiE diameter, preferably 0.5-1.2 mm, made of steel, glass, Contains ceramic, sand or plastic. Suitable agitator mills are for example in paint and varnish 71st, page 375 ff and Page 464 ff, paint and varnish 75, page 953 ff as well as in the German Auslegeschrift 1 230 657 described.

The pigments which can be incorporated into the claimed pigment preparations are not subject to any restriction. The intended use, e.g. in foams, requires special due to the high heat that generally occurs during production heat-resistant products. In addition, the pigments should make the foam. do not influence formation catalytically. The pigments can be organic or inorganic in nature. Suitable organic Pigments are, for example, those of the azo, anthraquinone, azaporphin, thioindigo series, as well as other polycyclic pigments, e.g. from the quinacridone, dioxazine, naphthalenetetracarboxylic acid, perylenetetracarboxylic acid or isoindolinone series as well as Efetallkoniplex pigments or laked dyes such as Ca, Mg, Al lacquers from sulfonic acid and / or carboxylic acid group-containing dyes, a large number of which are known, for example, from Color Index, 2nd edition. Suitable inorganic pigments are, for example Zinc sulphides, cadmium sulphides, cadmium selenides, ultramarine, Titanium dioxides, iron oxides, nickel or chromium antimony titanium oxides, cobalt blue, chromium oxides and chromate pigments as well as soot.

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Example 1

In 522 g of toluene diisocyanate, consisting of 80 % toluene-2,4-diisocyanate and 20 % toluene-2,6-diisocyanate, 390 g of n-octanol- (1 ) entered. After the reaction has ended, 134 g of methylolpropane are added at 140 ° C. over the course of 13 minutes. The temperature rises to 170 ⁰ C and this temperature is maintained for a further 30 minutes before Tributoxyäthylphosphat much is added that a "40% solution of the urethane resin is present in the organophosphate. In this solution, 28 % of a carbon black produced by the furnace process with a particle size of 56 ran on a funnel mill. A readily flowable carbon black paste is obtained which can be incorporated into polyurethane foams based on ethers or esters or into NCO group-containing, solvent-free or solvent-containing one-component lacquers without interference.

Example 2

684 g of 1-methylcyclohexanol- (2) are introduced into 1044 g of the toluene diisocyanate mixture from Example 1 with stirring, beginning at 125 ° C., over the course of 20 minutes. The temperature, which rises to 140 ° C., is then held for a further 10 minutes before a mixture of 134 g of methylolpropane and 219 g of 2-ethylhexanediol (1,3) is added. The heat of reaction causes the temperature to 170 ⁰ C rise, which is then maintained for another 30 minutes before the molten resin is poured into a pan. On a 40% solution of the resin in glycol monomethyl ether acetate, a viscosity of 28 centipoise is measured in a falling ball cosimeter according to the Hoppler method at 25.degree. With heating, the resin is dissolved in the adipic acid ester of diethylene glycol monoethyl ether. On a shaking device, 22.5 % of a furnace carbon black is dlsperglert with the aid of glass beads at 50 ^{0 C.}

This carbon black paste can also be used for coloring polyurethane foams and one-component paints containing MCO groups.
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Example 5

In 343 g of tolylene diisocyanate, consisting of 65 % tolylene-2,4-diisocyanate and 35 % tolylene-2,6-diisocyanate, 200 g of cyclohexanol are introduced within 20 minutes with stirring, starting at 125 ° C. The temperature, which has risen to 140 ° C. as a result of the heat of reaction, is held for a further 10 minutes before 104 g of 2,2-dimethyl-1,3-propanediol are added over the course of 15 minutes. The temperature, which rose to 165 ° C., is held for a further 30 minutes before the resin melt is poured into a tub to cool, viscosity of a 40% resin solution in glycol monomethyl ether acetate at 25 ° C. in a falling ball viscometer according to Höppler 25 centipoise. , _

In a 10% solution of the resin in a branched polyether with an average molecular weight of 4800, 10 % of a furnace carbon black with a BET surface area of 110 m / g is dispersed on a disk grinder. In addition, 10 % of the carbon black is dispersed in the polyether alone. The paste with the polyurethane | Despite the higher initial viscosity of the resin solution, resin is significantly more flowable than that of the pure polyether. Such a paste is particularly suitable for use in foam molding with polyether and diphenylmethane diisocyanate (4, V) as binders.

Example 4

In the same resin solution from Example 3 in a polyether, 10 % of a copper phthalocyanine of the α modification are dispersed in the same way. The flowable blue paste is well suited for coloring polyurethane foam on ether bacis.

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Example 5 T

In 50 g of a 10% solution of the polyurethane resin from Example 2 in a branched polyether with an average molecular weight of 3800 50 g of a titanium dioxide of the rutile form on a Corundum disk mill dispersed. The white paste is suitable alone or mixed with corresponding colored pastes for the j Use in polyurethane foam foaming.

Example 6

In 80 g of a 35% solution of the polyurethane resin from example 2 in diphenyl-2-ethylhexyl phosphate are 20 parts by weight of a stabilized copper phthalocyanine of the ^ modification dispersed on a corundum disk mill. A soft paste is obtained, which is equally suitable for coloring flexible polyurethane foams based on ether or ester.

Example 7

In 522 of the diisocyanate mixture of example 1 g are added under stirring starting from 100 ⁰ C, in 25 minutes 113 S Glykolrnonoäthyläther and then added 226 g n-octanol (l). After completion of the reaction at l40 ⁰ C ^13; + g trine thylolpropane added within 15 minutes. The rest of the reaction is carried out as in Example 1.

In 75 g of a 40 ^ igen solution of this resin in tributyl phosphate vjerden 25 g of furnace carbon black with an average particle size of 70 nm dispersed on a funnel mill. A flowable black paste is obtained, which is equally suitable for coloring polyurethane foams based on ethers or esters.

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Example 8

To 125 g of Dipb.enylmettLan-4,4 ^l -diisocyanate and 87 g of the loluylene diisocyanate mixture from Example 1 "are added 200 g of cyclohexanol within 25 minutes with stirring, starting at 125 ° C." The temperature of 150 ⁰ C is maintained for another 90 Hinuten before the melt is poured into a Yfanne. At 25 G in Kugelfallvislcosimeter by a coupler 40 follow solution of this resin in Glykolmonoinethylätherazetat has a viscosity of 10.5 centipoise.

In 75 g of a 50 / Sigen solution of the resin in a 2: 1 mixture leave from tributyl phosphate and diphenyl-2-ethylheryl phosphate 25 g of the furnace carbon black from Example 1 turned out to be very good Disperse flowable black paste on a corundum disk mill. Due to the wide compatibility of the resin, this black paste can be used in many ways for coloring polyurethane systems insert.

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Claims (6)

2407560 claims 1. Pigment pastes containing 3-80 % of an organic or inorganic pigment, 6-50 % low molecular weight polyurethane resins and 20-90% solvents and diluents free of amino groups and hydroxyl groups or containing them. 2. Pigment pastes containing 3 to 50 % of an organic pigment or carbon black or 20 to 80 % of an inorganic pigment, 6 to 50 % of low molecular weight polyurethane resins and 20 to 90 % of solvents and diluents. 3- pigment pastes according to claim 1, characterized in that that as polyurethane resins, reaction products of aromatic diisocyanates with polyols having 2 to 10 carbon atoms and monoalcohols with 6-8 carbon atoms, possibly mixed with shorter or longer chain monoalcohols or glycol monoethers be used. 4. pigment pastes according to claim 1, characterized in that 40 % ± ge solutions of the polyurethane resins in glycol monomethyl ether acetate have a viscosity of 10 to 120 centipoise. 5- Use of the pigment pastes according to claim 1 for pigmenting of synthetic, macromolecular materials. 6. With the pigment pastes according to claim. 1 pigmented synthetic, macromolecular materials. Le A 15 512 -9- 509839/1033