EP1409578A1 - Method of mass-colouring synthetic materials - Google Patents
Method of mass-colouring synthetic materialsInfo
- Publication number
- EP1409578A1 EP1409578A1 EP02767226A EP02767226A EP1409578A1 EP 1409578 A1 EP1409578 A1 EP 1409578A1 EP 02767226 A EP02767226 A EP 02767226A EP 02767226 A EP02767226 A EP 02767226A EP 1409578 A1 EP1409578 A1 EP 1409578A1
- Authority
- EP
- European Patent Office
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 229920002994 synthetic fiber Polymers 0.000 title claims abstract description 11
- 238000004040 coloring Methods 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 20
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 17
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 16
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 15
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 14
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims abstract description 14
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 14
- 229920001897 terpolymer Polymers 0.000 claims abstract description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 29
- 239000008187 granular material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- -1 methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy Chemical group 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- GPYLCFQEKPUWLD-UHFFFAOYSA-N 1h-benzo[cd]indol-2-one Chemical compound C1=CC(C(=O)N2)=C3C2=CC=CC3=C1 GPYLCFQEKPUWLD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- OUKFCUWFFHLVBM-UHFFFAOYSA-N buta-1,3-diene;prop-2-enamide;styrene Chemical compound C=CC=C.NC(=O)C=C.C=CC1=CC=CC=C1 OUKFCUWFFHLVBM-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000549 coloured material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005029 naphthylthio group Chemical group C1(=CC=CC2=CC=CC=C12)S* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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
- R 12 is hydrogen, a carboxylic acid group or a carboxylic acid ester group
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (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
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
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
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
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
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, 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
or
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
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
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
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
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
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02767226A EP1409578A1 (en) | 2001-07-26 | 2002-07-18 | Method of mass-colouring synthetic materials |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01810736 | 2001-07-26 | ||
| EP01810736 | 2001-07-26 | ||
| PCT/EP2002/007987 WO2003010229A1 (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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1409578A1 true EP1409578A1 (en) | 2004-04-21 |
Family
ID=8184054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02767226A Withdrawn EP1409578A1 (en) | 2001-07-26 | 2002-07-18 | Method of mass-colouring synthetic materials |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20040231073A1 (en) |
| EP (1) | EP1409578A1 (en) |
| JP (1) | JP2004536200A (en) |
| WO (1) | WO2003010229A1 (en) |
Family Cites Families (7)
| 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 |
| DE2428198C3 (en) * | 1974-06-11 | 1978-10-19 | Basf Ag, 6700 Ludwigshafen | Naphtholactam dyes, their production and dye preparations containing these dyes |
| CH614229A5 (en) * | 1975-02-28 | 1979-11-15 | Ciba Geigy Ag | |
| CA1085839A (en) * | 1976-06-01 | 1980-09-16 | Ciba-Geigy Ag | Naphtholactam dyestuffs |
| 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 |
-
2002
- 2002-07-18 WO PCT/EP2002/007987 patent/WO2003010229A1/en not_active Ceased
- 2002-07-18 US US10/484,355 patent/US20040231073A1/en not_active Abandoned
- 2002-07-18 JP JP2003515587A patent/JP2004536200A/en active Pending
- 2002-07-18 EP EP02767226A patent/EP1409578A1/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO03010229A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004536200A (en) | 2004-12-02 |
| WO2003010229A1 (en) | 2003-02-06 |
| US20040231073A1 (en) | 2004-11-25 |
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