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WO2003010229A1 - Method of mass-colouring synthetic materials - Google Patents

Method of mass-colouring synthetic materials Download PDF

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Publication number
WO2003010229A1
WO2003010229A1 PCT/EP2002/007987 EP0207987W WO03010229A1 WO 2003010229 A1 WO2003010229 A1 WO 2003010229A1 EP 0207987 W EP0207987 W EP 0207987W WO 03010229 A1 WO03010229 A1 WO 03010229A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
carboxylic acid
alkylthio
arylthio
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2002/007987
Other languages
French (fr)
Inventor
Peter Aeschlimann
Leonhard Feiler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to US10/484,355 priority Critical patent/US20040231073A1/en
Priority to EP02767226A priority patent/EP1409578A1/en
Priority to JP2003515587A priority patent/JP2004536200A/en
Publication of WO2003010229A1 publication Critical patent/WO2003010229A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/06—Naphtholactam dyes

Definitions

  • the present invention relates to a method of mass-colouring synthetic materials with dyes based on naphtholactam.
  • the present invention accordingly relates to a method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene (ABS terpolymers), which comprises using at least one dye of formula
  • R 2 is hydrogen, a carboxylic acid group or a carboxylic acid ester group
  • R 3 is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and
  • W is a radical of formula
  • R 4 , R 8 and Rn are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio,
  • R 5 , R 7 and R 10 are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group
  • R 6 and R 9 are each independently of the other cyano, -CONR 12 R 13 or -SO 2 R 14 , wherein R ⁇ 2 and R 13 are each independently of the other hydrogen or C C 4 alkyl and R 1 is C 1 -C 4 alkyl, and
  • X is -NH-, -O- or -S-, or
  • R 5 and R 5 ' together form a phenyl or naphthyl radical.
  • R 4 , R 8 and Rn as alkyl are each independently of the others preferably C C alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • R 12 , R 13 and R 14 as C C 4 alkyl are each independently of the others methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • R 1( R 3 , R 4 , R 5 , R 7 , Rs, R 1 0 and Rn as alkoxy are each independently of the others preferably C ⁇ -C alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, it being possible for the carbon chain in alkoxy to be interrupted one or more times by oxygen.
  • Ri, R 3 , R , R 5 , R 7 , R 8 , R 1 0 and Rn as alkylthio are each independently of the others preferably CrC alkylthio, for example methylthio, ethylthio, propylthio or butylthio.
  • Ri, R3, R , R5, R 7 , Rs, R10 and Rn as aryloxy are each independently of the others preferably C 6 -C- ⁇ 2 aryloxy, for example phenoxy or naphthyloxy.
  • R , R3, R , R5, R7, Rs, R 1 0 and R as arylthio are each independently of the others preferably C 6 -C 12 arylthio, for example phenylthio or naphthylthio.
  • phenyl radicals in phenoxy can be unsubstituted or substituted by methyl, chlorine, d-C 4 alkylthio and/or by arylthio.
  • naphthyl radicals in naphthyloxy can be unsubstituted or substituted by methyl, chlorine, C ⁇ -C 4 alkylthio and/or by arylthio.
  • Halogen is, for example, chlorine or iodine and preferably bromine.
  • a carboxylic acid group is to be understood as being a -(CH 2 ) n -COOH radical wherein n is a number from 0 to 3. n is preferably 0.
  • a carboxylic acid ester group is preferably a -(CH ⁇ n-COOCrCealkyl radical wherein n is a number from 0 to 3. n is preferably 0.
  • C C ⁇ Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl or hexyl.
  • Ri is preferably hydrogen, halogen or C C 4 alkylthio.
  • R 2 is preferably hydrogen, -COOH or -COOd-Cealkyl.
  • R 3 is preferably hydrogen, -COOH or -COOC C 6 alkyl.
  • R 4 is preferably hydrogen, CrC 4 alkyl, C C 4 alkoxy, C 1 -C 4 alkylthio, C 6 -C 12 aryloxy or C 6 -C 12 - arylthio.
  • R 5 is preferably hydrogen, -COOH, -COOC ⁇ C-ealkyl, C C alkyl, C C alkoxy, C ⁇ -C 4 alkylthio, C 6 -C 12 aryloxy or C 6 -C 12 arylthio.
  • R 6 is preferably cyano.
  • R 9 is preferably cyano.
  • X is preferably -O- and -S-.
  • R 12 is hydrogen, a carboxylic acid group or a carboxylic acid ester group
  • R 13 is hydrogen or C 6 -C ⁇ 2 aryIthio
  • Rn is a carboxylic acid group or a carboxylic acid ester group
  • R 15 and R 16 are each independently of the other hydrogen, CrC 4 alkoxy, C 6 -C 12 aryloxy,
  • Rl7 hydrogen, a carboxylic acid group or a carboxylic acid ester group, R-I8 s hydrogen or halogen, Rl9 s hydrogen,
  • X is -O- or -S-.
  • the dyes of formula (1) used in accordance with the invention are known, for example, from DE-A-2 736914, DE-A-2607 869, DE-A-2 724 566 and DE-A-2724 567 or can be prepared according to generally known methods.
  • the dyes of formula (1) used in accordance with the invention are prepared, for example, by condensing a naphtholactam compound of formula wherein
  • R-i, R 2 and R 3 are as defined for formula (1), in the presence of an acid condensation agent, preferably phosphorus oxychloride, with a methylene-active compound of formula
  • the compounds of formulae (50) to (52) are known or can be prepared according to generally known methods.
  • the present invention relates also to the use of the dyes of formula (1) in the production of coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material, which consists wholly or predominantly of ABS terpolymers or comprises ABS terpolymers, and a tinctorially effective amount of at least one dye of formula (1).
  • the colouring of such high molecular weight organic substances with the dye of formula (1) is carried out, for example, by mixing such a dye into those substrates using roll mills, mixing apparatus or grinding apparatus, with the result that the dye is dissolved or finely dispersed in the high molecular weight material.
  • the high molecular weight organic material with the admixed dye is then processed using processes known perse, for example calendering, compression moulding, extrusion, coating, spinning, casting or injection moulding, whereby the coloured material acquires its final form.
  • the admixing of the dye is carried out immediately prior to the actual processing step, for example by continuously feeding a solid, for example pulverulent, dye and, at the same time, a granulated or pulverulent high molecular weight organic material, and optionally also additional ingredients, e.g. additives, directly into the intake zone of an extruder, where mixing takes place just before processing.
  • a solid for example pulverulent, dye
  • a granulated or pulverulent high molecular weight organic material e.g. additives
  • additional ingredients e.g. additives
  • plasticisers In order to produce non-rigid mouldings or to reduce their brittleness, it is often desirable to incorporate so-called plasticisers into the high molecular weight compounds prior to shaping.
  • plasticisers for example, esters of phosphoric acid, phthalic acid or sebacic acid.
  • the plasticisers may be incorporated into the polymers before or after the incorporation of the colorant. It is also possible, in order to achieve different shades of colour, to add to the high molecular weight organic materials, in addition to the dye of formula (1), also further dyes, pigments or other colorants in any desired amounts, optionally together with further additives, e.g. fillers or siccatives.
  • thermoplastic plastics especially in the form of fibres or mouldings.
  • ABS terpolymer to be coloured comprises repeating monomer units of the formulae
  • the dyes used in accordance with the invention impart to the mentioned materials tinctorially strong, level red or orange colour shades having very good in-use fastness properties, especially good light fastness and good thermostability.
  • ABS acrylamide-butadiene-styrene terpolymer
  • the homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin,
  • the resulting yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.
  • ABS acrylamide-butadiene-styrene terpolymer
  • the homogenous mixture is extruded in an extruder (twin screw 25 mm from Collin,
  • the resulting orange- to yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

The present invention relates to a method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene, which comprises using at least one dye of formula (1) wherein R1 is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio, R2 is hydrogen, a carboxylic acid group or a carboxylic acid ester group, R3 is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and W is a radical of formulae (2), (3), (4), (5), (6), wherein R4, R8 and R11 are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio, R5, R7 and R10 are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, R6 and R9 are each independently of the other cyano, -CONR12R13 or -SO2R14, wherein R12 and R13 are each independently of the other hydrogen or C1-C4alkyl and R14 is C1-C4alkyl, and X is -NH-, -0- or -S-, or R5 and R5' together form a phenyl or naphthyl radical.

Description

Method of mass-colouring synthetic materials
The present invention relates to a method of mass-colouring synthetic materials with dyes based on naphtholactam.
The use of dyes of a wide variety of classes for the mass-colouring of synthetic materials is known. It has been shown, however, that not all synthetic materials can be coloured with satisfactory results with conventional dyes. Such "critical" synthetic materials also include materials based on terpolymers of acrylonitrile, butadiene and styrene which, owing to the very high temperatures that occur during processing and the heterogeneous structure, make specific demands of the dyes used. There is therefore a need for dyes with which such terpolymers (referred to hereinbelow as ABS terpolymers) can be mass-coloured in brilliant colour shades that are light-fast and fast to high temperatures.
It has now been found, surprisingly, that the naphtholactam dyes used in the method according to the invention meet the criteria given above to a considerable degree.
The present invention accordingly relates to a method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene (ABS terpolymers), which comprises using at least one dye of formula
Figure imgf000003_0001
wherein 1 is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio,
R2 is hydrogen, a carboxylic acid group or a carboxylic acid ester group,
R3 is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and
W is a radical of formula
Figure imgf000004_0001
wherein
R4, R8 and Rn are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio,
R5, R7 and R10 are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, R6 and R9 are each independently of the other cyano, -CONR12R13 or -SO2R14, wherein Rι2 and R13 are each independently of the other hydrogen or C C4alkyl and R1 is C1-C4alkyl, and
X is -NH-, -O- or -S-, or
R5 and R5' together form a phenyl or naphthyl radical.
R4, R8 and Rn as alkyl are each independently of the others preferably C C alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
R12, R13 and R14 as C C4alkyl are each independently of the others methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
R1( R3, R4, R5, R7, Rs, R10 and Rn as alkoxy are each independently of the others preferably Cι-C alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, it being possible for the carbon chain in alkoxy to be interrupted one or more times by oxygen.
Ri, R3, R , R5, R7, R8, R10 and Rn as alkylthio are each independently of the others preferably CrC alkylthio, for example methylthio, ethylthio, propylthio or butylthio.
Ri, R3, R , R5, R7, Rs, R10 and Rn as aryloxy are each independently of the others preferably C6-C-ι2aryloxy, for example phenoxy or naphthyloxy.
R , R3, R , R5, R7, Rs, R10 and R as arylthio are each independently of the others preferably C6-C12arylthio, for example phenylthio or naphthylthio.
The phenyl radicals in phenoxy can be unsubstituted or substituted by methyl, chlorine, d-C4alkylthio and/or by arylthio.
The naphthyl radicals in naphthyloxy can be unsubstituted or substituted by methyl, chlorine, Cι-C4alkylthio and/or by arylthio.
Halogen is, for example, chlorine or iodine and preferably bromine. A carboxylic acid group is to be understood as being a -(CH2)n-COOH radical wherein n is a number from 0 to 3. n is preferably 0.
A carboxylic acid ester group is preferably a -(CH^n-COOCrCealkyl radical wherein n is a number from 0 to 3. n is preferably 0.
C CβAlkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, pentyl or hexyl.
Ri is preferably hydrogen, halogen or C C4alkylthio.
R2 is preferably hydrogen, -COOH or -COOd-Cealkyl.
R3 is preferably hydrogen, -COOH or -COOC C6alkyl.
R4 is preferably hydrogen, CrC4alkyl, C C4alkoxy, C1-C4alkylthio, C6-C12aryloxy or C6-C12- arylthio.
R5 is preferably hydrogen, -COOH, -COOC^C-ealkyl, C C alkyl, C C alkoxy, Cι-C4alkylthio, C6-C12aryloxy or C6-C12arylthio.
R6 is preferably cyano.
R9 is preferably cyano.
X is preferably -O- and -S-.
For the method according to the invention, preference is given to the dyes of formula
Figure imgf000007_0001
wherein
R12 is hydrogen, a carboxylic acid group or a carboxylic acid ester group,
R13 is hydrogen or C6-Cι2aryIthio,
Rn is a carboxylic acid group or a carboxylic acid ester group, and
R15 and R16 are each independently of the other hydrogen, CrC4alkoxy, C6-C12aryloxy,
CrC4alkylthio or C6-C12arylthio, and of formula
Figure imgf000007_0002
wherein
Rl7 s hydrogen, a carboxylic acid group or a carboxylic acid ester group, R-I8 s hydrogen or halogen, Rl9 s hydrogen,
R2o s cyano, R2ι s hydrogen or C -C^alkyl, R22 s a carboxylic acid group or a carboxylic acid ester group, and
X is -O- or -S-.
For the method according to the invention, special preference is given to the dyes of formulae
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
The dyes of formula (1) used in accordance with the invention are known, for example, from DE-A-2 736914, DE-A-2607 869, DE-A-2 724 566 and DE-A-2724 567 or can be prepared according to generally known methods.
The dyes of formula (1) used in accordance with the invention are prepared, for example, by condensing a naphtholactam compound of formula
Figure imgf000013_0001
wherein
R-i, R2 and R3 are as defined for formula (1), in the presence of an acid condensation agent, preferably phosphorus oxychloride, with a methylene-active compound of formula
Figure imgf000013_0002
or
Figure imgf000013_0003
wherein
Re, 7, Rs and X are as defined for formula (3), and R9, Ri0 and R are as defined for formula (4).
The compounds of formulae (50) to (52) are known or can be prepared according to generally known methods.
The present invention relates also to the use of the dyes of formula (1) in the production of coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material, which consists wholly or predominantly of ABS terpolymers or comprises ABS terpolymers, and a tinctorially effective amount of at least one dye of formula (1).
The colouring of such high molecular weight organic substances with the dye of formula (1) is carried out, for example, by mixing such a dye into those substrates using roll mills, mixing apparatus or grinding apparatus, with the result that the dye is dissolved or finely dispersed in the high molecular weight material. The high molecular weight organic material with the admixed dye is then processed using processes known perse, for example calendering, compression moulding, extrusion, coating, spinning, casting or injection moulding, whereby the coloured material acquires its final form. It is also possible for the admixing of the dye to be carried out immediately prior to the actual processing step, for example by continuously feeding a solid, for example pulverulent, dye and, at the same time, a granulated or pulverulent high molecular weight organic material, and optionally also additional ingredients, e.g. additives, directly into the intake zone of an extruder, where mixing takes place just before processing. In general, however, it is preferable for the dye to be mixed into the high molecular weight organic material beforehand, because more even coloration of the substrates can be obtained.
In order to produce non-rigid mouldings or to reduce their brittleness, it is often desirable to incorporate so-called plasticisers into the high molecular weight compounds prior to shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. In the method according to the invention the plasticisers may be incorporated into the polymers before or after the incorporation of the colorant. It is also possible, in order to achieve different shades of colour, to add to the high molecular weight organic materials, in addition to the dye of formula (1), also further dyes, pigments or other colorants in any desired amounts, optionally together with further additives, e.g. fillers or siccatives.
Preference is given to the colouring of thermoplastic plastics, especially in the form of fibres or mouldings.
The ABS terpolymer to be coloured comprises repeating monomer units of the formulae
Figure imgf000015_0001
which may be linked to one another randomly, in an alternating manner or in the form of block or graft polymers.
The dyes used in accordance with the invention impart to the mentioned materials tinctorially strong, level red or orange colour shades having very good in-use fastness properties, especially good light fastness and good thermostability.
The following Examples serve to illustrate the invention. Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.
Example 1 :
1200.00 g of an acrylamide-butadiene-styrene terpolymer (ABS) (Teriuran 877M from BASF) are mixed homogeneously with
2.4 g of the dye of formula
Figure imgf000016_0001
in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin,
D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 200°C, cooled with water, granulated in a granulator (Scheer, Stuttgart) and then dried in a granule drier (Turb
Etuve TE 25 from MAPAG AG, CH-3001 Bern) for 4 hours at 60°C.
The resulting yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.
Example 2:
By following the procedure of Example 1 but using, instead of 2.4 g of the dye of formula (9), the same amount of one of the dyes of formulae (10) to (28), there are likewise obtained coloured ABS granules which are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.
Example 3:
1200.00 g of an acrylamide-butadiene-styrene terpolymer (ABS) (Teriuran 877M from BASF) are mixed homogeneously with
2.4 g of the dye of formula
Figure imgf000016_0002
and
12.0 g of TiO2 (Kronos 2220) in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.
The homogenous mixture is extruded in an extruder (twin screw 25 mm from Collin,
D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 200°C, cooled with water, granulated in a granulator (Scheer, Stuttgart) and then dried in a granule drier (Turb
Etuve TE 25 from MAPAG AG, CH-3001 Bern) for 4 hours at 60°C.
The resulting orange- to yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.
Example 4:
By following the procedure of Example 3 but using, instead of 2.4 g of the dye of formula (28), the same amount of one of the dyes of formulae (9) to (27), there are likewise obtained coloured ABS granules which are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties.

Claims

What is claimed is:
1. A method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene, which comprises using at least one dye of formula
Figure imgf000018_0001
wherein
Ri is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio,
R2 is hydrogen, a carboxylic acid group or a carboxylic acid ester group,
R3 is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and
W is a radical of formula
Figure imgf000018_0002
Figure imgf000019_0001
wherein
R4) R8 and Rn are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio,
R5> R7 and R10 are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group,
R6 and R9 are each independently of the other cyano, -CONR12Ri3 or -SO2R14, wherein R12 and R13 are each independently of the other hydrogen or C C4alkyl and R14 is Cι-C4alkyl, and
X is -NH-, -O- or -S-, or
R5 and R5' together form a phenyl or naphthyl radical.
2. A method according to claim 1, wherein R4, R8 and R as alkyl are CrC4alkyl.
3. A method according to claim 1, wherein R^ R3, R4) R5, R7, R8, R10 and Rn as alkoxy are d-C4alkoxy.
4. A method according to claim 1, wherein R1f R3l R , R5) R7, R8, Rio and Rn as alkylthio are d-C4alkylthio.
5. A method according to claim 1, wherein R1f R3, R4, R5, R7, R8, Rio and R as aryloxy are C6-Cι2aryloxy.
6. A method according to claim 1, wherein Ri, R3, R4, R5, R7, R8, R10 and Rn as arylthio are C6-Cι2arylthio.
7. The use of a dye of formula (1) according to claim 1 in the mass-colouring of synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene.
8. A synthetic material based on a terpolymer of acrylonitrile, butadiene and styrene coloured according to any one of claims 1 to 7 with a dye of formula (1 ) according to claim 1.
PCT/EP2002/007987 2001-07-26 2002-07-18 Method of mass-colouring synthetic materials Ceased WO2003010229A1 (en)

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US10/484,355 US20040231073A1 (en) 2001-07-26 2002-07-18 Method of mass-colouring synthetic materials
EP02767226A EP1409578A1 (en) 2001-07-26 2002-07-18 Method of mass-colouring synthetic materials
JP2003515587A JP2004536200A (en) 2001-07-26 2002-07-18 How to knead and color synthetic materials

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EP01810736 2001-07-26

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DE2415055A1 (en) * 1974-03-28 1975-10-02 Bayer Ag Metal complexes of 2-substd naphtho-pyrrolidine dyes - with higher thermal stability, for use in plastics, lacquers and textiles
US4009165A (en) * 1974-06-11 1977-02-22 Basf Aktiengesellschaft Naphtholactam dyes
US4256896A (en) * 1976-06-01 1981-03-17 Ciba-Geigy Aktiengesellschaft Naphtholactam dyestuffs

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CH614229A5 (en) * 1975-02-28 1979-11-15 Ciba Geigy Ag
US4246410A (en) * 1976-06-01 1981-01-20 Ciba -Geigy Aktiengesellschaft Naphtholactam dyestuffs
US4180665A (en) * 1976-06-01 1979-12-25 Ciba-Geigy Aktiengesellschaft Substituted 3-benz(cd)indol-2-(1H)-ylidene-furo[2,3-b]quinoxalin-2(3H)one dyestuffs
LU75606A1 (en) * 1976-08-17 1978-04-13

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Publication number Priority date Publication date Assignee Title
DE2415055A1 (en) * 1974-03-28 1975-10-02 Bayer Ag Metal complexes of 2-substd naphtho-pyrrolidine dyes - with higher thermal stability, for use in plastics, lacquers and textiles
US4009165A (en) * 1974-06-11 1977-02-22 Basf Aktiengesellschaft Naphtholactam dyes
US4256896A (en) * 1976-06-01 1981-03-17 Ciba-Geigy Aktiengesellschaft Naphtholactam dyestuffs

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