DD301159A7 - Black pigments, preferably for camouflage purposes - Google Patents

Abstract

Black pigments, preferably for camouflage purposes with IR radiation-reflecting properties for reflecting the reflectivity in the IR region, consist of perylenetetracarboxylic diimide dyes. Use of the perylenetetracarboxylic acid diimide dyestuffs according to the invention alone or mixed with one another or further pigments in paints, polyvinyl chloride, polyethylene, polyurethane, special printing inks and pigment preparations. The resulting dyeings are excellent light and weather, excellent overcoating and solvent and softening. The infrared remission values allow by admixing z. B. green and yellow pigments, the remission curve of the leaf greens (chlorophyll increase) to exactly mimic or by admixing other pigments z. B. the remission curves of sand, soil, concrete, mortar u. Ä. Adjust. The resulting military camouflage effect compared to special recording techniques is a decisive feature of the black pigments according to the invention.

Description

= -NH-CT

and NH-CN ^N NH-CO-NH ₂

NH

NH

> NH ₂

OH

R = -H, -CI-NO _{2 can be used} alone or in admixture with conventional camouflage pigments.

For this 7 pages drawings

Field of application of the invention

The invention relates to new black pigments and is preferably suitable for camouflage purposes with IR radiation-reflecting properties.

Characteristic of the known technical solutions

In DT-AS 2,451,780, the Ν, Ν'-bis-Y-hydroxypropyl-imide and the N, N'-bis-n-propylimide and in DT-AS 2.451.783 the N, N'-bis-ß Phenyläthylimid of perylenetetracarboxylic called as IR-radiopaque black pigments. These pigments mimic the reflectivity of the leaf green (chlorophyll) in the IR region only imperfectly. DT-PS 975.121 discloses di- and trianthrimides of the anthraquinone series, such as the (4 ', 4 "-bis benzoylamino) -1,1', 5,1" -trianthrimide, as IR radiation-reflecting black pigments for paints. These pigments are characterized by a complicated synthesis and low solvent, overcoating and plasticizer fastness.

Object of the invention

The aim of the invention is to find black pigments that allow optimal military camouflage effect by irritation of the reflectivity of the leaf green in the IR region and have high fastness to solvents, Weichmacl ren and recoating.

Explanation of the essence of the invention

Object of the invention

The object of the invention is to provide new black pigment formulations.

Features of the invention

According to the invention the object is achieved in that compounds of the general formula

X-N

in the X = -CH ₂ -CH (OH) -CH ₃

= -CH ₂ -CH ₂ -OH = -CH ₂ -CH ₂ -NH ₂

NH

NH-CN -NH

= -C

= -c

NH

and ~ C

N-X

NH NH-CO-NH

NH

R = -H, -Cl-NO ₂

be used as a black pigment, preferably for camouflage purposes.

The perylenetetracarboxylic diimide dyes known here can be used as IR-radiopaque black pigments alone or in admixture with one another or with other pigments in coating materials, polyvinyl chloride, polyethylene, polyurethane, but also in

special inks and used in pigment preparations.

The resulting military camouflage effect is a decisive feature for the pigments mentioned.

The black pigments may also be subjected to formation such as precipitation from sulfuric acid or salt milling

become.

The dyeings obtained with the pigments of the invention are excellent light and weather, excellent overcoating and solvent and softening. The infrared remission values allow by admixing z. Green and yellow pigments, to exactly mimic the remtoslone curve of the leaf greens; by mixing with other inorganic and / or organic pigments (eg., lead sulfochromate, a-Eisenoxydhydrat, a-Eison-lll-oxide, Chromoxidgrün, titanium dioxide, monoazo, phthalocyanines, mixed phase pigments) and / orextendern (eg aluminum silicate, aluminum hydroxide silicate) is obtained eg Brown, gray and olive colors of different shades with a very good camouflage effect compared to special recording techniques.

embodiments

example 1

1 part of the black pigment perylenetetracarboxylic acid-N.N'-bis-methoxy-n-propylimide is ground with 4 parts of a medium-viscosity chlorinated rubber coating in a stirred ball mill, with glass beads with a diameter of 0.7 mm serve as grinding media. After a dispersion time of 10 minutes, the glass beads are separated and the material to be rubbed is diluted 1:10 with unpainted i.ack. The resulting varnish is cast with a Keyl cast film box to form a wet film 200pm thick. After drying, the film is measured for its IR reflectance behavior by Beckman spectrophotometer DK 2 A (see FIG. 1).

FIG. 1 shows a black pigment based on perylenetetracarboxylic acid-N.N'-bis-methoxy-n-propyl imide according to DE-AS 2451781.

Example 2

Working according to Example 1 and uses perylenetetracarboxylic acid Ν, Ν'- to 3 "-methylpyrazolon-1" -N-carbamidide, we obtain a film which gives the curve 2 after measurement (see Figure 2).

Example 3

Working according to Example 1, uses perylenetetracarboxylic acid-N.N'-bis-dicyandiamidid and uses a PUR varnish, we obtain a black paint or a black film, which shows curve 3 after measurement (see Figure 3).

Example 4

100 parts of PVC powder, 2 parts of a plasticizer, z. B. dioctyl phthalate, and 0.1 part of the black pigment Perylentetracarbonsäure bis-NN-ß-aminoethyl imide be homogenized on a mixing mill at 16O ⁰ C for 10min. The resulting rolled sheet is formed at 175 ° C by a calender to 1 mm thick film. The black film results in measuring an IR remission curve curve 4 (see Figure 4).

Examples 5-7

Using Example 4 and using the pigments of Examples 1-3, one also obtains black films corresponding to the IR reflectance words given in Curves 1-3.

Example 8

0.4 parts of the pigment from Example 4 are mixed dry in a drum mixer with 100 parts of polyethylene H powder, then granulated at 180 ⁰ C via an extruder and processed in the film blowing machine at 200 ⁰ C to a black 250 pm thick film. The foil also gives the values of the curve 4 after the measurement.

Example 9

If you work according to Example 4 and are still 0, L 'parts Chromoxidgrün added, we obtain an olive-colored foil.

Example 10

If one operates according to Example 4, but uses 0.1 part Helioechtschwarz IRK, we obtain a black film, which, however, significantly lower solvent and softener ripples results and thus exhibits lower remission stability.

Example 11

If the black pigments according to the invention are formulated with chromium oxide green (Color Index: Pigmont green 17 No. 77 288), a-iron oxide hvdrat (Color Index: Pigment Yellow 42 No. 77492), yellow pigments with high IR remission (for example monoazo pigments [Color Index: Pigment Yellow 97), mixed-phase pigments of the system Ti-Sb-Cr-oxides having Pi itil structure [CoIo 'Index: Pigment Yellow 118 No. 77894], lead sulfochromates [Color Index: Pigment Yellow 34 No. 77603]), a-iron-I d (Color Index: Pigment Red 101 No. 77491), titanium dioxide (Color Index: Pigment White 6) to a dark green pigment door of the following form 0.20 to 8 parts black pigment according to the invention

1.0 to 20 parts yellow pigment with high IR remission

0.02 to 20 parts of o-iron oxide hydrate

5.0 to 60 parts of chromium oxide green

0.1 to 8 parts of ferric iron oxide

1.0 to 20 parts of titanium dioxide,

where the sum of the pigments is 100 parts in each case, remission curves are obtained which correspond to the natural environment (leaf green, dark) in the range λ = 400 nm to λ = 1200 nm.

A konk ^r etes example corresponds to the following combination:

0.27 parts black pigment

1.55 parts of Novoperm yellow FGL (Hoechst AG, Frankfurt [M.] - FRG) 0.04 parts of Eisenoxidgelb 214501 (VEB Kali-Chemie, Berlin) 5.82 parts of Chromoxidgrün (Sojuschimexport SU) 0.15 parts Bayferrox 140 (Bayer AG, Leverkusen - FRG) 2.75 parts of titanium dioxide Kronos RN57P (Kronos-Titan GmbH, Leberkusen - FRG) (see Figure 5).

Example 12

The black pigments according to the invention are formulated with α-iron-III oxide (Color Index: Pigment Red 101 No. 77491), carbon black (Color Index: Pigment Black No. 7,499) and a yellow pigment with high IR remission (eg α-iron oxide hydrate (Color Index: pigment Gelb42 Nr.77492] Mischphasenpigmento the system Ti-Sb-Cr oxides with a rutile structure [Color Index: pigment Yellow 118 Nr.77894], yellow monoazo pigment [Color Index: pigment Yellow 9 ⁷ lead sulfochromates [Color Index: Pigmont Yellow 34 No. 77 603]), titanium dioxide (Color Index: Pigment White 6) to a light brown pigment formulation of the following form 1 to 10 parts of black pigment according to the invention 1 to 70 parts of a-iron-lll-oxide

0.1 to 2.5 parts of carbon black

35 to 75 parts of yellow pigment with high IR remission 30 to 75 parts of titanium dioxide,

the sum of the pigments is in each case 100 parts. Thus, remission curves are obtained which correspond to the natural environment (sand, soil, rock) in the range λ = 400 nm to 1200 μm. A concrete example corresponds to the following combination:

5.57 parts black pigment according to the invention 1.22 parts iron oxide red N 203/2 (VEB Kali-Chemie Nerchau) 0.59 parts channel black Orga E Piv. (VEB Rußwerke Oranienburg) 92.63 parts Sicotangelb L2111 (BASF inks + fibers Ag, Stuttgart) 55.57 parts of Kronos RN57P titanium dioxide (Kronos-Titan GmbH, Leverkusen - FRG) (see FIG. 6).

Example 13

If the black pigments according to the invention are formulated with α-iron oxide hydrate (Color Index: Pigment Yellow 42 No. 77492), iron II, III oxide (Color Index: Pigment Black 11 No. 77499), a yellow pigment with high IR remission (eg lead sulfochromate [cf. Color Index: Pigment Yellow 34 No. 77 894], mixed phase pigment of the system Ti-Sb-Cr oxides with rutile structure [Color Index: Pigment GeIb118 No.77894], yellow monoazo pigment (Color Index: Pigment Yellow 97]), titanium dioxide (Color Index Pigment white 6) and aluminum hydroxide silicate to give a pigmented pigment formulation of the following form 0.25 to 15 parts of black pigment according to the invention 20 to 60 parts of a-iron oxide hydrate 1 to 25 parts of iron-ILIII-oxide

1 to 25 parts of yellow pigment with high IR remission 20 to 75 parts titanium dioxide 15 to 60 parts of aluminum hydroxide silicate, wherein the sum of the pigments with the extender is 100 parts, we obtain remission curves in the range of λ = 400ηm to 1200nm which correspond to the concrete B300. A concrete example corresponds to the following pigmentation:

0.54 parts black pigment according to the invention

2.70 parts chrome yellow GM25 (Ten Horn, Farben-Chemie, Maastricht-Holland) 12.59 parts iron oxide yellow 214501 (VEB Kaü-Chemie Berlin) 1.44 parts iron oxide black (VE3 Kali-Chemie Nerchau) 55.75 parts titanium dioxide Anatas LO- CR (Sechtleben-Chemie GmbH, Duisburg - FRG) 24.98 parts of kaolin Anka (VEB silicate raw material Kombinat Kemmlitz) (see FIG. 7)

Claims (1)

Black pigment, preferably for use with IR radiation-reflecting properties, characterized in that perylenetetracarboxylic diimide dyes of the general formula O ti ο o in the X = -CH ₂ -CH (OH) -CH ₃ = -CH ₂ -CH ₂ -OH = -CH ₂ -CH ₂ -NH ₂