CA2045331A1 - Perylenetetracarboxylic acid diimides containing long-chain alkanoylamino radicals - Google Patents
Perylenetetracarboxylic acid diimides containing long-chain alkanoylamino radicalsInfo
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- CA2045331A1 CA2045331A1 CA002045331A CA2045331A CA2045331A1 CA 2045331 A1 CA2045331 A1 CA 2045331A1 CA 002045331 A CA002045331 A CA 002045331A CA 2045331 A CA2045331 A CA 2045331A CA 2045331 A1 CA2045331 A1 CA 2045331A1
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- perylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Perylenetetracarboxylic acid diimides containing long-chain alkanoylamino radicals Abstract of the Disclosure Compounds of formula (I), wherein R is C7-C21alkyl, C4-C18alkenyl, C5-C12cycloalkyl or C5-C6cycloalkyl-substituted C1-C4alkyl, R1, R2, R3 and R4 are each independently of one another hydrogen, chloro, bromo, methyl or methoxy, Z is a direct bond or-O-, -S-, -NH-, -CO-, -SO2- or -NHCO-, and n is 0 or 1.
These compounds have excellent suitability as pigments for colouring organic material of high molecular weight, especially polyvinyl chloride, polyolefins and paints.
These compounds have excellent suitability as pigments for colouring organic material of high molecular weight, especially polyvinyl chloride, polyolefins and paints.
Description
2 0 ~ 3 ~
P-l 8133/A
Pervlenetetracarboxvlic acid diimides containin~ lon~-chain alkanoylamino radicals The present invention relates to perylenetetracarboxylic acid diimides containing long-chain cyclic or unsaturated alkanoylamino radicals which are attached to both N-atoms through aromatic nuclei, and to the use thereof for colouring organic material of high molecular weight.
N,N'-Dialkylperylene-3,4,9, 1 0-tetracarboxylic acid diimides containing long-chain alkyl radicals for colouring polyolefins are disclosed in US patent specification 4 238 386.
These compounds are unsatisfactory on the one hand because of their tendency to blooming and, on the other, because their wet~astness properties do not meet all the current requirements of pigment technology.
Perylene-3,4,9,10-tetracarboxylic acid diirnides which are substituted at both N-atoms by lower alkanoylamino groups, and the use thereof for colouring paints, coating materials and plastics, are disclosed in US patent specification 2 462 851. These pigments too do not meet all of the increasingly stringent requirements for specific applications.
lt is disclosed in EP-A û 283 436 that coloured polyolefins with enhanced properties can be obtained by using peTylenetetracarboxylic acid diiTnides containing long-chain aliphatic radicals which carry carboxyl or earbamoyl groups attached to both N-atoms.
There have now been found novel perylenetetracarboxylic acid diimides which contain long-chain cyclic or unsaturated alkanoylamino radicals attached to both N-atoms through aromatic nuclei and which, surprisingly, colour organic material of high molecular weight in shades of enhanced fastness properties.
Specifically, the invention relates to compounds of formula ~ ~ 3 ?3 ~ + I~lHCo ;~
wherein R is C7-C21alkyl, C4-CI8alkenyl, C5-CI2cycloalkyl or Cs-C6cycloalkyl-substituted Cl-C4alkyl, Rl, R2, R3 and R4 are each independently of one another hydrogen, chloro, bromo, methyl or methoxy, Z is a direct bond or -O-, -S-, -N~-, -CO-, -SO2- or -NHCO-, and n isOor 1.
R as C7-C21alkyl is s~raight-chain or branched alkyl and is typically n-heptyl, 1-, 2-, 3- s)r 4-methylhexyl, 1,1- or 3,4-dimethylpentyl, 1- or 3-ethylpentyl, 1,3,3- and 2,4,4-trimethylbutyl, 1-ethyl-3-methylbutyl, 1-propylbutyl, I-methyl-1-ethylbutyl, 1-propyl-2-methylpropyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, n-octyl, 2-, 3-, 4-, 5- or 6-methylheptyl, I,1-dimethylhexyl, 1,5-dimethylhexyl, 1-ethylhexyl, 1-ethyl-2-methylpentyl, 1-ethyl-1-methylpentyl, 1-ethyl-4-methylpentyl, 1-isopropylpentyl, 1,1,3,3-tetramethylbutyl, 2,2,3,3-tetramethylbutyl, I-isopropyl-3-methylbutyl, nonyl, decyl, 1-neopentyl-3,3-dimethylbutyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyl or eneicosyl.
R as C4-Cl~alkenyl may also be straight-chain or branched alkenyl and is typically 1-, 2-or 3-butenyl, I-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 1,3-butadienyl, 1-, 2-, 3- or 4-pentenyl, 1-methyl-1-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 1,3-pentadienyl, 3-methyl-1,3-butadienyl, 3- or 5-hexenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 4-methyl-3-pentenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 1- or 6-heptenyl, 1-ethyl-1-pentenyl, 1-ethyl-2-pentenyl, 2,3,3-trimethyl-1-butenyl, 1- or 7-octenyl, 2-methyl-1-octenyl, 2-methyl-2-octenyl, ~-decenyl or 8-heptadecenyl.
- 2~ 33~
R as Cs-CI2cycloalkyl may be cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl.
R as Cs-C6cycloalkyl-substituted Cl-C4alkyl may be cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylpropyl, cyclopentylbutyl or cyclohexylbutyl.
Particularly important compounds of formula I are those wherein n is 0 and, among these, more particularly those compounds wherein Rl and R2 are hydrogen.
Preferred compounds are compounds of formula ~N ~I~HCO-R (Il) wherein R is Cl2-Cl8alkyl.
The compounds of formula I can be prepared by methods which are sommonly known.
Conveniently they are obtained in two synthesis steps starting from perylene-3t4,9,10-tetracarboxylic acid or the anhydride thereof, for example by an initial condensation with an amino group of a diamine of ~orrnula H2N $Z~NH2 (111), wherein Rl, R2, R3, R4 and n are as defined above, and then by a second condensation of the resultant diaminodiimide with a carbonyl chloride of formula R-C\ ~IV), wherein R is as defined above, in accordance with ~he following reaction scheme:perylene-3,4,9,10-tetracarboxylic acid or anhydride + at least 2 H2N--~Z~Nllz ~ R
+ at least ~0 2 R-C\
Cl ~f ~ ~3'~
P-l 8133/A
Pervlenetetracarboxvlic acid diimides containin~ lon~-chain alkanoylamino radicals The present invention relates to perylenetetracarboxylic acid diimides containing long-chain cyclic or unsaturated alkanoylamino radicals which are attached to both N-atoms through aromatic nuclei, and to the use thereof for colouring organic material of high molecular weight.
N,N'-Dialkylperylene-3,4,9, 1 0-tetracarboxylic acid diimides containing long-chain alkyl radicals for colouring polyolefins are disclosed in US patent specification 4 238 386.
These compounds are unsatisfactory on the one hand because of their tendency to blooming and, on the other, because their wet~astness properties do not meet all the current requirements of pigment technology.
Perylene-3,4,9,10-tetracarboxylic acid diirnides which are substituted at both N-atoms by lower alkanoylamino groups, and the use thereof for colouring paints, coating materials and plastics, are disclosed in US patent specification 2 462 851. These pigments too do not meet all of the increasingly stringent requirements for specific applications.
lt is disclosed in EP-A û 283 436 that coloured polyolefins with enhanced properties can be obtained by using peTylenetetracarboxylic acid diiTnides containing long-chain aliphatic radicals which carry carboxyl or earbamoyl groups attached to both N-atoms.
There have now been found novel perylenetetracarboxylic acid diimides which contain long-chain cyclic or unsaturated alkanoylamino radicals attached to both N-atoms through aromatic nuclei and which, surprisingly, colour organic material of high molecular weight in shades of enhanced fastness properties.
Specifically, the invention relates to compounds of formula ~ ~ 3 ?3 ~ + I~lHCo ;~
wherein R is C7-C21alkyl, C4-CI8alkenyl, C5-CI2cycloalkyl or Cs-C6cycloalkyl-substituted Cl-C4alkyl, Rl, R2, R3 and R4 are each independently of one another hydrogen, chloro, bromo, methyl or methoxy, Z is a direct bond or -O-, -S-, -N~-, -CO-, -SO2- or -NHCO-, and n isOor 1.
R as C7-C21alkyl is s~raight-chain or branched alkyl and is typically n-heptyl, 1-, 2-, 3- s)r 4-methylhexyl, 1,1- or 3,4-dimethylpentyl, 1- or 3-ethylpentyl, 1,3,3- and 2,4,4-trimethylbutyl, 1-ethyl-3-methylbutyl, 1-propylbutyl, I-methyl-1-ethylbutyl, 1-propyl-2-methylpropyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, n-octyl, 2-, 3-, 4-, 5- or 6-methylheptyl, I,1-dimethylhexyl, 1,5-dimethylhexyl, 1-ethylhexyl, 1-ethyl-2-methylpentyl, 1-ethyl-1-methylpentyl, 1-ethyl-4-methylpentyl, 1-isopropylpentyl, 1,1,3,3-tetramethylbutyl, 2,2,3,3-tetramethylbutyl, I-isopropyl-3-methylbutyl, nonyl, decyl, 1-neopentyl-3,3-dimethylbutyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyl or eneicosyl.
R as C4-Cl~alkenyl may also be straight-chain or branched alkenyl and is typically 1-, 2-or 3-butenyl, I-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-1-propenyl, 1,3-butadienyl, 1-, 2-, 3- or 4-pentenyl, 1-methyl-1-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 1,3-pentadienyl, 3-methyl-1,3-butadienyl, 3- or 5-hexenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 4-methyl-3-pentenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 1- or 6-heptenyl, 1-ethyl-1-pentenyl, 1-ethyl-2-pentenyl, 2,3,3-trimethyl-1-butenyl, 1- or 7-octenyl, 2-methyl-1-octenyl, 2-methyl-2-octenyl, ~-decenyl or 8-heptadecenyl.
- 2~ 33~
R as Cs-CI2cycloalkyl may be cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl.
R as Cs-C6cycloalkyl-substituted Cl-C4alkyl may be cyclopentylmethyl, cyclohexylmethyl, cyclopentylethyl, cyclohexylpropyl, cyclopentylbutyl or cyclohexylbutyl.
Particularly important compounds of formula I are those wherein n is 0 and, among these, more particularly those compounds wherein Rl and R2 are hydrogen.
Preferred compounds are compounds of formula ~N ~I~HCO-R (Il) wherein R is Cl2-Cl8alkyl.
The compounds of formula I can be prepared by methods which are sommonly known.
Conveniently they are obtained in two synthesis steps starting from perylene-3t4,9,10-tetracarboxylic acid or the anhydride thereof, for example by an initial condensation with an amino group of a diamine of ~orrnula H2N $Z~NH2 (111), wherein Rl, R2, R3, R4 and n are as defined above, and then by a second condensation of the resultant diaminodiimide with a carbonyl chloride of formula R-C\ ~IV), wherein R is as defined above, in accordance with ~he following reaction scheme:perylene-3,4,9,10-tetracarboxylic acid or anhydride + at least 2 H2N--~Z~Nllz ~ R
+ at least ~0 2 R-C\
Cl ~f ~ ~3'~
~ ~ ~Z ~ NtlCO 1 The diamines of forrnula III are known compounds, most of which are commerciallyavailable.
:~ .
The carbonyl chlorides of formula IV can be conveniently prepared by known methods ~rom the corresponding known carboxylic acids, most of which are also commercially available, typically by reaction with thionyl chloride. However, it is also possible to react the free acid direct or a lower alkyl ester thereof.
The condensation reactions can be calTied out by comrnonly employed methods, forexample in the presence of an organic solvent or, if one of the reactants is used as solvent, under normal or elevated pressure, with or without a catalyst.
Illustrative examples of suitable solvents for the initial condensation to form the corresponding perylene diimides starting from perylene-3,4,9,10-tetracarboxylic acid or the dianhydride thereof are water, dimethyl formamide, N-methylpyrrolidone, quinoline, glycols such as ethylene glycol or propylene glycol, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and its isomers or diacetone alcohol, as well as aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and trichlorobenzenes, toluene and xylenes.
Suitable solvents for the second condensation reaction are typically cyclohexane, aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and trichlorobenænes, toluene, xylenes, cumene and tert-butylbenzene.
,.....
~,~
2~3~
:~ .
The carbonyl chlorides of formula IV can be conveniently prepared by known methods ~rom the corresponding known carboxylic acids, most of which are also commercially available, typically by reaction with thionyl chloride. However, it is also possible to react the free acid direct or a lower alkyl ester thereof.
The condensation reactions can be calTied out by comrnonly employed methods, forexample in the presence of an organic solvent or, if one of the reactants is used as solvent, under normal or elevated pressure, with or without a catalyst.
Illustrative examples of suitable solvents for the initial condensation to form the corresponding perylene diimides starting from perylene-3,4,9,10-tetracarboxylic acid or the dianhydride thereof are water, dimethyl formamide, N-methylpyrrolidone, quinoline, glycols such as ethylene glycol or propylene glycol, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and its isomers or diacetone alcohol, as well as aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and trichlorobenzenes, toluene and xylenes.
Suitable solvents for the second condensation reaction are typically cyclohexane, aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichloro- and trichlorobenænes, toluene, xylenes, cumene and tert-butylbenzene.
,.....
~,~
2~3~
If one reactant is used direct as solvent (in excess) in the condensation reactions, then the reaction medium is diluted, after complete amide formation, preferably with one of the organic solvents cited above until the excess component is present in solution. The residual suspension is then filtered, and the excess component can be recovered from the filtrate by evaporation of the solvent.
A further means of preparing the compounds of formula I comprises condensing perylene-3,4,9,10-tetracarboxylic dianhydride in general accordance with the commonly employed methods described above with an amine of formula H2N ~ NHCO R (V) in the molar ratio 1:2.
The amines of forrnula V are known or they can be prepared by conventional methods.
The perylene diimides obtained in the practice of this invention are isolated and dried by conventional methods. They h~sve excellent suitability as pigments for colouring organic material of high molecular weight.
Illustrative examples of organic materials of high molecular weight which can be coloured with the pigments of this invention are cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, typically polymerisation or condensation resins, such as aminoplasts, preferablyurea/formaldehyde and melamine/formaldehyde resins, aLtcyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and silicone resins, singly or in mixtures.
The above high molecular weight organic compounds may be singly or as mixtures in the form of plastics, melts or of spinning solutions, paints, coating materials or printing inks.
Depending on the end use requirement, it is expedient to use the pigments of the invention , -- 2 ~
as ~oners or in the form of preparations.
The pigments of this invention are especially suitable for mass colouring polyvinyl chloride and, preferably, polyole~lns such as polyethylene and polypropylene, as well as for pigmenting paints and coating materials, more particularly automotive lacquers and, among these, preferably metallic paints.
The pigments of the invention can be used in an amount of 0.01 so 30 % by weight, preferably 0.1 to 10 % by weigh~ based on the high molecular weight organic material.
The pigmenting of the high molecular weight organic materials ~vith the pigments of this invention is effected conveniently by incorporating the pigments by themselves or in the form of masterbatches in the substrates using roll mills, mixing or milling apparatus. The pigmented material is then brought into the desired final form by methods which are known per se, conveniently by calendering, moulding, extruding, coating, spinning, casting or by injection moulding. It is often desirable to incorporate plasticisers into the high molecular weight compounds before processing in order to produce non-brittle mouldings or to diminish their brittleness. Suitable plasticisers are typically esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated before or after working the pigments into the polymers. To obtain different shades it is also possible to add fillers or other chromophoric components such as white, coloured or black pigments, in any amount to the high molecular weight organic materials.
For pigmenting paints, coating materials and printing inks, the high molecular weight organic materials and the pigments of the invention, together with optional additives such as fillers, other pigments, siccatives or plasticisers, are ~1nely dispersed or dissolved in a common organic solvent or solvent mixture. The procedure may be such that the individual components by themselves, or also several jointly, are dispersed or dissolved in the solvent and thereafter all the components are rnixed.
When used for colouring conveniently e.g. polyvinyl chloride or polyolefins, the pigments of this invention have good general pigment properties, such as good dispersibility, high colour strength and purity, as well as excellent fastness to migration, heat, light and weathering. They have particularly good suitability for pigmenting paints for producing metallic effect ~1nishes. In addition, they have excellent resistance to acid.
The invention is illustrated by the following Examples.
Example 1: 10 ml of pyridine are added to a mixture of 14.25 g of N,N'-bis(4-amino-phenyl)perylenetetracarboxylic acid diimide and 27.75 g of stearoyl chloride in 500 ml of o-dichlorbenzene, and the mixture is heated to 140C. The dark red suspension is stilred for 6 hours at this temperature and afterwards cooled to 80C and filtered. The poduct is washed in succession with 100 ml of o-dichlorobenzene, 1000 ml of hot alcohol and 1000 ml of hot water, and dried at 60C in a vacuum drier to give 25.55 g (92.4 % of theory) of a red pigment of formula ~ N11CO~CHz)~jCH3 in powder form, which colours polyethylene, polyvinyl chloride and polyamide in strong red shades of excellent fastness to migration, heat and light.
Analysis:
cal.: (in %): C 78.23 H 8.02 N 5.07 found: (in %): C 77.86 H 7.84 N 4.84.
Examples 2-16: Further pigments can be prepared by the method described in Example 1 by acylating each of the diarnines listed in column I of the following Table with the acid chloride listed in column II in the molar ratio 1:2. Column III indicates ~he shade of the PVC sheet coloured with the resultant pigments in accordance with subsequent Example 17.
~d ~3~
g Ex. II III
2 N,N'-bis(4-aminophenyl)perylene- decanoyl chloride red tetracarboxylic acid diimide 3 N,N'-bis(4-aminophenyl)perylene- 3-cyclopentylpropionyl orange red tetracarboxylic acid diimide chloride 4 N,N'-bis(4-aminophenyl)perylene- lauroyl chloride red tetracarboxylic acid diimide N,N'-bis(4-aminophenyl)perylene- undecanoyl chloride red tetracarboxylic acid diimide 6 N,N'-bis(4-aminophenyl)perylene- tetradecanoyl chloride red tetracarboxylic acid diimide 7 N,N'-bis(4-aminophenyl)perylene- heptanoyl chloride red tetracarboxylic acid diimide 8 N,N'-bis(4-aminophenyl)perylene- octanoyl chloride red tetracarboxylic acid diimide 9 N,N'-bis(4-aminophenyl)perylene- pelargonyl chloride orange red tetracarboxylic acid diimide N,N'-bis(4-arninophenyl)perylene- palmitoyl chloride red tetracarboxylic acid diimide 11 N,N'-bis(4-aminophenyl)perylene- 10-undecenoyl chloride dark red tetracarboxylic acid diimide 12 N,N'-bis(4-aminophenyl)perylene- oleyl chloride red tetracarboxylic acid diimide 13 N,N'-bis(2,5-dimethyl-4-amino- stearoyl chloride orange phenyl)perylenetetracarboxylic acid diimide 14 N,N'-bis(2,5-dimethyl-4-amino- lauroyl chloride orange phenyl)perylenetetracarboxylic acid diimid N,N'-bis(2,5-dirnethyl-4-amino- oleyl chloride orange phenyl)perylenetetracarboxylic acid diimide 16 N,N'-bis(3-aminophenyl)perylene- lauroyl chloride red tetracarboxylic acid diimide . _ - lo -Example 17: 40 mg of the perylene diimide pigment according to Example 1,7.3 rnl of dioctyl phthalate and 13.3 g of stabilised polyvinyl chloride (~)LONZA E-722 arethoroughly mixed in a glass beaker with a glass rod, and the mixture is processed to a thin sheet on a roll mill for 5 minutes at 160C. The PVC sheet so obtained is coloured in a strong red shade of high purity and very good lightfastness. The dispersibility of the pigment is excellent.
Example 18: A mixture of 1.0 g of the perylene diimide pigment obtained according to Example 1, 1.0 g of antioxidant ~)IRGANOX 1010 (CIBA-GEIGY AG) and 1000 g of HD
polyethylene granules ((~)VESTOLEN A60-16, HUELS) is stirred for 15 minutes in a3 litre glass bottle on a roller gear table. The mixture is then extruded in two passes in a single screw extruder. The granulate so obtained is moulded to boards at 250C in an injection moulding machine ((~)Allround Aarburg 200)for 5 minutes. The mouldings are coloured in a strong, level red shade of high purity and excellent lightfastness.
Example 19: 1000 g of polypropylene granules (~DAPLEN PT-55, Chernie LINZ) and 1.0 g of the perylene diimide pigment obtained according to Exarnple 1 are rnixed for 15 minutes in a 3 litre bottle on a roller gear bed. The mixture is subsequently extruded twice through a single-screw extruder and then granulated. The granules so obtained are spun at 280-285C by the melt spinning process. The red filaments have very goodlightfastness and excellent textile properties, such as rubfastness and wetfastness to detergents and solvents. The pigment has excellent heat resistance during the spinning process at 285C.
Example 20: The process described in Example 18 is repeated, but using, in addition to the coloured pigment, 10 g of titanium dioxide ~KRONOS RN-57-P (KRONOS Titan GmbH), to give red pressed sheets having comparably good heat resistance. The pressed sheets, which are injection moulded at 200-2oOC, exhibit no colour deviations after cooling.
Example 21: A mixture of 130 g of steatite balls (0 = 8 mm), 45.5 g of a thermosetting acrylic varnish consisting of 41.3 g of acrylic resin ~g)VIACRYL VC 373, 60 % (VIANOVA Kunstharz AG), 2 0 ~
16.3 g of melamine resin (~)MAPRENAL l'rX, 55 % (HOECHST AG), 32.8 g of xylene, 4.6 g of ethyl glycol acetate, 2.0 g of butyl acetate and 1.0 g of (~)silicone oil A, 1 % in xylene (BAYER AG), and 2.5 g of the perylene diimide obtained in Example I
is dispersed in a 200 ml glass bottle with twist-off stopper for 72 hours on a roller gear bed. The steatite balls are removed and then 8.0 g of the dispersed masstone mixture, 0.6 g of alun~inium paste ~ALCOA, (60-65 % Al content, Aluminium Corp. of America), 1.0 g of methyl ethyl ke.one and 18.4 g of the above therrnosetting acrylic varnish are thoroughly mixed, and the mixture is sprayed on to alurninium sheets and subsequently baked for 30 minutes at 130C, to give very strong red metallic effect finishes of excellent fastness properties.
A further means of preparing the compounds of formula I comprises condensing perylene-3,4,9,10-tetracarboxylic dianhydride in general accordance with the commonly employed methods described above with an amine of formula H2N ~ NHCO R (V) in the molar ratio 1:2.
The amines of forrnula V are known or they can be prepared by conventional methods.
The perylene diimides obtained in the practice of this invention are isolated and dried by conventional methods. They h~sve excellent suitability as pigments for colouring organic material of high molecular weight.
Illustrative examples of organic materials of high molecular weight which can be coloured with the pigments of this invention are cellulose ethers and esters, such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins, typically polymerisation or condensation resins, such as aminoplasts, preferablyurea/formaldehyde and melamine/formaldehyde resins, aLtcyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, ABS, polyphenylene oxides, rubber, casein, silicone and silicone resins, singly or in mixtures.
The above high molecular weight organic compounds may be singly or as mixtures in the form of plastics, melts or of spinning solutions, paints, coating materials or printing inks.
Depending on the end use requirement, it is expedient to use the pigments of the invention , -- 2 ~
as ~oners or in the form of preparations.
The pigments of this invention are especially suitable for mass colouring polyvinyl chloride and, preferably, polyole~lns such as polyethylene and polypropylene, as well as for pigmenting paints and coating materials, more particularly automotive lacquers and, among these, preferably metallic paints.
The pigments of the invention can be used in an amount of 0.01 so 30 % by weight, preferably 0.1 to 10 % by weigh~ based on the high molecular weight organic material.
The pigmenting of the high molecular weight organic materials ~vith the pigments of this invention is effected conveniently by incorporating the pigments by themselves or in the form of masterbatches in the substrates using roll mills, mixing or milling apparatus. The pigmented material is then brought into the desired final form by methods which are known per se, conveniently by calendering, moulding, extruding, coating, spinning, casting or by injection moulding. It is often desirable to incorporate plasticisers into the high molecular weight compounds before processing in order to produce non-brittle mouldings or to diminish their brittleness. Suitable plasticisers are typically esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated before or after working the pigments into the polymers. To obtain different shades it is also possible to add fillers or other chromophoric components such as white, coloured or black pigments, in any amount to the high molecular weight organic materials.
For pigmenting paints, coating materials and printing inks, the high molecular weight organic materials and the pigments of the invention, together with optional additives such as fillers, other pigments, siccatives or plasticisers, are ~1nely dispersed or dissolved in a common organic solvent or solvent mixture. The procedure may be such that the individual components by themselves, or also several jointly, are dispersed or dissolved in the solvent and thereafter all the components are rnixed.
When used for colouring conveniently e.g. polyvinyl chloride or polyolefins, the pigments of this invention have good general pigment properties, such as good dispersibility, high colour strength and purity, as well as excellent fastness to migration, heat, light and weathering. They have particularly good suitability for pigmenting paints for producing metallic effect ~1nishes. In addition, they have excellent resistance to acid.
The invention is illustrated by the following Examples.
Example 1: 10 ml of pyridine are added to a mixture of 14.25 g of N,N'-bis(4-amino-phenyl)perylenetetracarboxylic acid diimide and 27.75 g of stearoyl chloride in 500 ml of o-dichlorbenzene, and the mixture is heated to 140C. The dark red suspension is stilred for 6 hours at this temperature and afterwards cooled to 80C and filtered. The poduct is washed in succession with 100 ml of o-dichlorobenzene, 1000 ml of hot alcohol and 1000 ml of hot water, and dried at 60C in a vacuum drier to give 25.55 g (92.4 % of theory) of a red pigment of formula ~ N11CO~CHz)~jCH3 in powder form, which colours polyethylene, polyvinyl chloride and polyamide in strong red shades of excellent fastness to migration, heat and light.
Analysis:
cal.: (in %): C 78.23 H 8.02 N 5.07 found: (in %): C 77.86 H 7.84 N 4.84.
Examples 2-16: Further pigments can be prepared by the method described in Example 1 by acylating each of the diarnines listed in column I of the following Table with the acid chloride listed in column II in the molar ratio 1:2. Column III indicates ~he shade of the PVC sheet coloured with the resultant pigments in accordance with subsequent Example 17.
~d ~3~
g Ex. II III
2 N,N'-bis(4-aminophenyl)perylene- decanoyl chloride red tetracarboxylic acid diimide 3 N,N'-bis(4-aminophenyl)perylene- 3-cyclopentylpropionyl orange red tetracarboxylic acid diimide chloride 4 N,N'-bis(4-aminophenyl)perylene- lauroyl chloride red tetracarboxylic acid diimide N,N'-bis(4-aminophenyl)perylene- undecanoyl chloride red tetracarboxylic acid diimide 6 N,N'-bis(4-aminophenyl)perylene- tetradecanoyl chloride red tetracarboxylic acid diimide 7 N,N'-bis(4-aminophenyl)perylene- heptanoyl chloride red tetracarboxylic acid diimide 8 N,N'-bis(4-aminophenyl)perylene- octanoyl chloride red tetracarboxylic acid diimide 9 N,N'-bis(4-aminophenyl)perylene- pelargonyl chloride orange red tetracarboxylic acid diimide N,N'-bis(4-arninophenyl)perylene- palmitoyl chloride red tetracarboxylic acid diimide 11 N,N'-bis(4-aminophenyl)perylene- 10-undecenoyl chloride dark red tetracarboxylic acid diimide 12 N,N'-bis(4-aminophenyl)perylene- oleyl chloride red tetracarboxylic acid diimide 13 N,N'-bis(2,5-dimethyl-4-amino- stearoyl chloride orange phenyl)perylenetetracarboxylic acid diimide 14 N,N'-bis(2,5-dimethyl-4-amino- lauroyl chloride orange phenyl)perylenetetracarboxylic acid diimid N,N'-bis(2,5-dirnethyl-4-amino- oleyl chloride orange phenyl)perylenetetracarboxylic acid diimide 16 N,N'-bis(3-aminophenyl)perylene- lauroyl chloride red tetracarboxylic acid diimide . _ - lo -Example 17: 40 mg of the perylene diimide pigment according to Example 1,7.3 rnl of dioctyl phthalate and 13.3 g of stabilised polyvinyl chloride (~)LONZA E-722 arethoroughly mixed in a glass beaker with a glass rod, and the mixture is processed to a thin sheet on a roll mill for 5 minutes at 160C. The PVC sheet so obtained is coloured in a strong red shade of high purity and very good lightfastness. The dispersibility of the pigment is excellent.
Example 18: A mixture of 1.0 g of the perylene diimide pigment obtained according to Example 1, 1.0 g of antioxidant ~)IRGANOX 1010 (CIBA-GEIGY AG) and 1000 g of HD
polyethylene granules ((~)VESTOLEN A60-16, HUELS) is stirred for 15 minutes in a3 litre glass bottle on a roller gear table. The mixture is then extruded in two passes in a single screw extruder. The granulate so obtained is moulded to boards at 250C in an injection moulding machine ((~)Allround Aarburg 200)for 5 minutes. The mouldings are coloured in a strong, level red shade of high purity and excellent lightfastness.
Example 19: 1000 g of polypropylene granules (~DAPLEN PT-55, Chernie LINZ) and 1.0 g of the perylene diimide pigment obtained according to Exarnple 1 are rnixed for 15 minutes in a 3 litre bottle on a roller gear bed. The mixture is subsequently extruded twice through a single-screw extruder and then granulated. The granules so obtained are spun at 280-285C by the melt spinning process. The red filaments have very goodlightfastness and excellent textile properties, such as rubfastness and wetfastness to detergents and solvents. The pigment has excellent heat resistance during the spinning process at 285C.
Example 20: The process described in Example 18 is repeated, but using, in addition to the coloured pigment, 10 g of titanium dioxide ~KRONOS RN-57-P (KRONOS Titan GmbH), to give red pressed sheets having comparably good heat resistance. The pressed sheets, which are injection moulded at 200-2oOC, exhibit no colour deviations after cooling.
Example 21: A mixture of 130 g of steatite balls (0 = 8 mm), 45.5 g of a thermosetting acrylic varnish consisting of 41.3 g of acrylic resin ~g)VIACRYL VC 373, 60 % (VIANOVA Kunstharz AG), 2 0 ~
16.3 g of melamine resin (~)MAPRENAL l'rX, 55 % (HOECHST AG), 32.8 g of xylene, 4.6 g of ethyl glycol acetate, 2.0 g of butyl acetate and 1.0 g of (~)silicone oil A, 1 % in xylene (BAYER AG), and 2.5 g of the perylene diimide obtained in Example I
is dispersed in a 200 ml glass bottle with twist-off stopper for 72 hours on a roller gear bed. The steatite balls are removed and then 8.0 g of the dispersed masstone mixture, 0.6 g of alun~inium paste ~ALCOA, (60-65 % Al content, Aluminium Corp. of America), 1.0 g of methyl ethyl ke.one and 18.4 g of the above therrnosetting acrylic varnish are thoroughly mixed, and the mixture is sprayed on to alurninium sheets and subsequently baked for 30 minutes at 130C, to give very strong red metallic effect finishes of excellent fastness properties.
Claims (7)
1. A compound of formula (I), wherein R is C7-C21alkyl, C4-C18alkenyl, C5-C12cycloallcyl or C5-C6cycloalkyl-substituted C1-C4alkyl, R1, R2, R3 and R4 are each independently of one another hydrogen, chloro, bromo, methyl or methoxy, Z is a direct bond or -O-, -S-, -NH-, -CO-, -SO2- or -NHCO-, and n is 0 or 1.
2. A compound of formula I according to claim 1, wherein n is 0.
3. A compound of formula I according to claim 2, wherein R1 and R2 are hydrogen.
4. A compound according to claim 1 of formula (II), wherein R is C12-C18alkyl.
5. Organic material of high molecular weight pigmented with a compound of formula I
according to claim 1.
according to claim 1.
6. Organic material of high molecular weight according to claim 5, which is a polyolefin.
7. Organic material of high molecular weight according to claim 5, which is a paint.
FD 4.3/BUE/sf*
FD 4.3/BUE/sf*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2143/90-6 | 1990-06-27 | ||
| CH214390 | 1990-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2045331A1 true CA2045331A1 (en) | 1991-12-28 |
Family
ID=4226880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002045331A Abandoned CA2045331A1 (en) | 1990-06-27 | 1991-06-25 | Perylenetetracarboxylic acid diimides containing long-chain alkanoylamino radicals |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0465410B1 (en) |
| JP (1) | JPH04226161A (en) |
| KR (1) | KR920005716A (en) |
| CA (1) | CA2045331A1 (en) |
| DE (1) | DE59101768D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19805121A1 (en) | 1998-02-09 | 1999-08-12 | Basf Ag | Process for the preparation of dye-containing, aqueous polymer dispersions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE562588A (en) * | ||||
| US2668815A (en) * | 1951-05-24 | 1954-02-09 | Gen Aniline & Film Corp | Vat dyestuffs of the perylenetetracarboxylic acid bis-arylimide series |
| EP0006122B1 (en) * | 1978-05-18 | 1982-04-28 | Ciba-Geigy Ag | Process for batch-colouring hard pvc and polyolefines |
| DE2832761B1 (en) * | 1978-07-26 | 1979-10-31 | Basf Ag | Process for converting crude and / or coarsely crystallized perylene tetracarboxylic diimides into a pigment form |
| US4379934A (en) * | 1980-01-19 | 1983-04-12 | Basf Aktiengesellschaft | Process for two-dimensionally concentrating light, and novel perylene-3,4,9,10-tetracarboxylic acid diimides |
| EP0283436B1 (en) * | 1987-03-13 | 1991-01-16 | Ciba-Geigy Ag | Perylene-tetracarboxylic-acid diimides with long-chain residue containing carbonyl groups |
-
1991
- 1991-06-18 DE DE59101768T patent/DE59101768D1/en not_active Expired - Fee Related
- 1991-06-18 EP EP91810466A patent/EP0465410B1/en not_active Expired - Lifetime
- 1991-06-24 KR KR1019910010421A patent/KR920005716A/en not_active Application Discontinuation
- 1991-06-25 CA CA002045331A patent/CA2045331A1/en not_active Abandoned
- 1991-06-27 JP JP3156611A patent/JPH04226161A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04226161A (en) | 1992-08-14 |
| DE59101768D1 (en) | 1994-07-07 |
| KR920005716A (en) | 1992-04-03 |
| EP0465410B1 (en) | 1994-06-01 |
| EP0465410A1 (en) | 1992-01-08 |
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