CA2338126A1 - Process for bulk dyeing of plastics - Google Patents
Process for bulk dyeing of plastics Download PDFInfo
- Publication number
- CA2338126A1 CA2338126A1 CA002338126A CA2338126A CA2338126A1 CA 2338126 A1 CA2338126 A1 CA 2338126A1 CA 002338126 A CA002338126 A CA 002338126A CA 2338126 A CA2338126 A CA 2338126A CA 2338126 A1 CA2338126 A1 CA 2338126A1
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- Prior art keywords
- substituted
- alkyl
- independently
- unsubstituted
- formula
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229920003023 plastic Polymers 0.000 title claims abstract description 16
- 239000004033 plastic Substances 0.000 title claims abstract description 16
- 238000004043 dyeing Methods 0.000 title claims abstract description 10
- 239000000975 dye Substances 0.000 claims abstract description 46
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000000732 arylene group Chemical group 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 3
- -1 1,3-phenylene, 1,4-phenylene Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- 150000001448 anilines Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 230000022244 formylation Effects 0.000 claims description 3
- 238000006170 formylation reaction Methods 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910019213 POCl3 Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000009747 press moulding Methods 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
-
- 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
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Coloring (AREA)
- Artificial Filaments (AREA)
Abstract
A process for the bulk dyeing of plastics, characterized in that use is made of dyes of the formula (I)
Description
Le A 34 197-Foreign Countries Her/ngb/NT
Process for bulk dyeing of plastics The invention relates to a process for bulk dyeing of plastics, characterized in that use is made of dyes of the formula (I) R2 R2.
NC - ~ ~ R4 R4' ~ ~ CH=C/CN
R1 C-CH N-Y-N ~ ~R~~ (I) R3 R3, where Y is a bivalent radical selected from the group consisting of substituted and unsubstituted arylenes and alkylenes, where the alkylene radicals may, if desired, have interruption by heteroatoms, such as O or S, Rl and R1', independently of one another, are an electron-withdrawing group, preferably cyano or alkoxycarbonyl, in particular C1-C4-alkoxycarbonyl, R2, R2', R3 and R3', independently of one another <~re hydrogen, alkyl, in particular Cl-C4-alkyl, CF3 or halogen, preferably F or Cl, R4 and R4', independently of one another, are un.substituted or substituted alkyl, preferably C1-C6-alkyl, or C~-C12-aralkyl, preferably benzyl.
In one preferred embodiment, Y represents unsubstituted or substituted phenylene, or unsubstituted or substituted C1-C6-alkylene, and examples of particularly preferred radicals Y
are: 1,3-phenylene, 1,4-phenylene or methyl-substituted 1,3- or 1,4-phenylene, ~-CH2-CH2-, -CH2CH2CH2-, -(CH2)4-, -CH2CH(CH3)-, -CH2CH2-O-CH2CH2- and -CH2CH2-S-CH2;CH2-.
Le A 34 197-Foreign Countries Very particular preference is given to alkylene radicals, in particular -t:H2CH2-, -(CH2)3-, -(CH2)4-, and -CH2CH2-O-CH2CH2-.
Examples of preferred radicals Rl and Rl' are: -CN, -C02CH3, -C02CH2CH3, -CO2(CH2)2CH3 and -C02(CHZ)3CH3.
Examples of preferred radicals R2, R2', R3 and R3' axe hydrogen, methyl, ethyl, Cl, F, CF3, methoxy and ethoxy.
Examples of preferred radicals R4 and R4' are CH3, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
In one preferred embodiment, R1 = R1', R2 = R2', R3 = R3' and R4 = R4' in formula (I) in the use according to the invention.
It is particularly preferable to use dyes of the formula (Ia) Rz R2 NC C-CH ~ \ N-Y-N ~ \~-CH=C~
Ri ~ R1 (Ia) where Y is unsubstituted or substituted phenylene, in particular 1,3- or 1,4-phenylene, or unsubstituted or substituted C2-C6-al:kylene, in particular ethylene, propylene or butylene, ' CA 02338126 2001-02-23 Le A 34 197-Foreign Countries R1 is CN, C02CH3, C02CH2CH3 or COZ(CH2)3CH3, R2 is hydrogen, CH3 or CH2CH3, and R4 is CH3, CH2CH3, n-propyl or n-butyl.
Preference is likewise given to the use of dyes of the. formula (I) where at least one of the substituent pairs Rl/Ri~, R2/R2', R3/R3' and R'4/R4~ is non-identical (e.g.. Rl ~
Rl'). These asymmetric dyes of the formula (I) are also provided by this invention.
For the purposes of this application, bulk dyeing is in particular processes in which the dye of the formula (I) is incorporated into the molten plastic material, e.g. with the aid of an extruder, or in which the dye is added straight away to the starting materials for preparing the plastic, e.g. to the monorr~ers, prior to polymerization.
The approximate processing temperatures here are from 100 to 380°C.
Some of the dyes to be used according to the invention are known (e.g. CH-516 628, JP-A 02 292 371), and others may be prepared by analogy with processes known from the literature. An example of a preparation is a. Vilsmeier formylation followed by condensation with a reactive methylene compound, preferably malononitrile.
A preferred preparation is the condensation of a substituted aniline with a di-halogenoalkylene (Eq. 1) Le A 34 197-Foreign Countries R2 R2, Ra Ra, rt I
NH + X (CH2)n X + HN ~ ~ (Eq. 1 ) R3 R3, Rz R2 Ra Ra N-(CH2)~ N
-HX
R2 R2.
a R
NH + X-(CH2)~ IJ ~ ~ (Eq.2) R3 R3, where n is from 2 to 6, and X represents halogen, in particular Cl or Br, and the other substituents are as defined above, or condensation of a substituted aniline with an N-(halogenoalkyl)aniline (Eq.
2), for example in a solvent or in bulk, in the presence o P a base, followed by Vilsmeier formylation (preferably by reacting with POCl3 and dimethylformamide, followed by hydrolysis), followed by condensation with a :reactive methylene compound, preferably malononitrile.
Examples which may be mentioned of suitable thermoplastics are: cellulose esters, such as cellulose nitrate, cellulose acetate, cellulose triacetate, cellulose acetobutyrate Le A 34 197-Foreign Countries -S-and cellulose propionate, cellulose ethers, such as rnethylcellulose, ethylcellulose and benzylcellulose, linear saturated polyester resins;, aniline resins, polycarbonates, polystyrene, polyvinylcarbazole, polyvinyl chloride, in particular unplasticized PVC, polymethacrylates, polyvinylidene chloride, polya~crylonitrile, polyoxymethylenes, linear polyurethanes, and also copolymers, such as vinyl chloride-vinyl acetate copolymers, and also in particular styrene copolymers, such as styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers (SB) and styrene-oc-methylstyrene copolymers (SMS) and acrylonitrile-butadiene-styrene copolymers (ABS).
The high-molecular-weight compounds mentioned may be present individually or in mixtures, as plastic materials or melts; which may be spun to give fibres, if desired.
The novel process is particularly suitable for bullk dyeing of polystyrene, and in particular for bulk dyeing of poly(meth)acrylat:es, and preferably polymethyl methacrylate SAN, SMS, ABS, or else polyethylene terephthalate or polybutylene terephthalate.
It is expedient for the plastics to be dyed to be in the form of powders, chips or pellets and to be mixed intimately with the dye. One method of achieving this is by coating the plastic particles with the finely divided dry pulverulent dye, or by treating the particles with a solution or dispersion of the dye in an organic solvent and then removing the solvent.
The process of the invention may also use mixtures of different dyes of the formula (I) and/or mixtures of dyes of the formula (I) with other dyes and/or with inorganic or organic pigments.
The dyes of the formula (I) are preferably in their solid form, in particular pulverulent or granular, when used according to the invention.
Le A 34 197-Foreign Countries S
These solid dye preparations comprise at least 95~% by weight, preferably at least 98% by weight, in particular more than 99% by wei~;ht, of dye of the formula (I) and, if desired, up to 5% by weight of organic binder, in each case based on the dye preparation.
These dye preparations are also provided by the invention.
Examples of possible binders are ethylene oxide-propylene oxide block copolymers, preferably those with a molar mass of from 4000 to L 6,000 g/mol.
When used for dyeing, the dye preparations are in particular preferably in the form of powders, in particular in the form of dry powders which have been ground and screened, or else are in the form of pellets, such as those which may be prepared in accordance with EP-A-488 933, for example.
The ratio of dye to plastic can vary within wide limits, depending on the desired colour strength. It is generally advisable to use from 0.005 to 5% by weight, preferably from 0.01 to 2% by weight, of dye, based on the amount of the plastic to be dyed.
Corresponding high-quality opaque colourings can be obtained by adding pigments insoluble in the polymers, e.g. titanium dioxide.
Examples of the amounts of titanium dioxide which can be used are from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the amount of polymer.
The treated polymer particles are melted by known processes in an extruder and extruded to give articles such as films or fibres, or cast to give sheets.
Le A 34 197-Foreign Countries _7_ One way of dyeing the plastics with the dyes of thc~ formula (I) is to admix a dye of this type, if desired in the form of a masterbatch, with these substrates using roll mills, mixing equipment or grinding equipment. T'he dyed material is then brought into its desired final form by processes known per se, such as calandering, S compression moulding, extruding, spreading, casting or inj ection moulding.
It is often desirable to incorporate what are known as plasticizers into the high-molecular-weight compounds prior to shaping, in order to produce non-rigid mouldings or to reduce the brittleness of the same. Examples of the plasticizers which can be used are esters of phosphoric acid, ph.thalic acid or sebacic acid. In the process of the invention, the plasticizers may be iincorporated prior to or after the incorporation of the dye into the polymers. It is rr~oreover possible for any desired amounts of fillers and/or other colouring constituents, such as white pigments, colour pigments or black pigments, to be added alongside the compounds of the formula (I) to the high-molecular-weight organic substances in order to achieve different shades.
The resultant greenish-to reddish-yellow colourings have good light resistance and good weathering resistance. The dyes of the invention are also very heat-fast within the thermoplastics.
Le A 34 197-Foreign Countries _g_ Example 1 0.1 g of the dye of the formula CH3 i H3 NC CHZ CH2 , CN
C=CH / \ N-CH2 CHZ N ~ \ CH=C~
NC CN (A) and 2 g of titanium dioxide (Bayertitan~ R-FK-2), and 100 g of a pelletized polystyrene are mixed for 2 hours in a sealed container on a roller bed. The resultant mixture is extruded at about 230°C to extrudates of width 2 cm and repelletized. The pellets are injection moulded at from 230 to 240°C. This gives reddish-yellow-coloured mouldings with high light resistance and high brilliance.
Example 2 0.02 g of the dye of the formula (A) and 100 g of a :pelletized polystyrene are mixed for 2 hours in a sealed container on a roller bed. The resultant mixture is then injection moulded at from 230°C to 240°C, using an injection-moulding machine with a screw, to give mouldings. The yellow-coloured, transparent mouldings have high lightfastness.
Example 3 If the dye of the formula (I) is replaced by the dye of the formula (B) ' CA 02338126 2001-02-23 Le A 34 197-Foreign Countries NC ~ ~ ~ ~ ,CN
C=CH N (CH2)4 N CH=C~
NC CN
CH3 CH3 (B) and the procedure is otherwise as described in Example 1, yellow-coloured mouldings with high lightfastness are obtained.
S
Example 4 If 0.035 g of the dye of the formula (B) and 100 ;g of a pelletized polystyrene are mixed and the procedure is otherwise as described in Example 2, yellow-coloured, transparent mouldings with high lightfastness are obtained.
Example 5 0.03 g of dye of the formula (A) are dissolved in '99.97 g of methyl metr~acrylate.
After addition of 0.01 g of dibenzoyl peroxide the solution is heated to 120°C and the polymerization initiated. After 30 minutes, the methyl methacrylate which has begun to polymerize is placed between two glass plates and the polymerization completed for 10 hours at 80°C. This gives yellow-colouref., transparent polymethyl meth-acrylate sheets.
Example 6 0.02 g of dye of the formula (B) and 100 g of polymethyl methacrylate are mixed dry and homogenized in a twin-screw extruder at 240°C. The material discharged as extrudate is pelletized. It is then shaped by press-moulding. This gives a transparent, yellow-coloured plastic with very good lightfastness and weather fastness.
Le A 34 197-Foreign Countries Example 7 100 g of a commercially available polycarbonate in the form of pellets are mixed dry with 0.01 g of solid of the formula (A). The resull:ant pellets are homogenized in a twin-screw extruder at 350°C. This gives a transparent, yellow coloration with good lightfastness. The dyed polycarbonate is discharged as extrudate and pelietized. The pellets may be processed by customary thermoplastic processing methods.
Example 8 0.04 g of solid of the formula (B) are mixed dry with 100 g of styrene-acrylonitrile copolymer and homogenized in a twin-screw extruder at 190°C and pelletized, and may then be shaped in the usual way by press-moulding. This gives a transparent, coloured plastic with good lightfastness. If 1% of titanium dioxide is added during the operation an opaque coloration is obtained.
Example 9 If in Example 1 the dye of the formula (A) is replace-d by the dye of the formula (CH2)3 CH3 NC / ' ~~ ,CN
C=CH N-CH2 CH2 N ~ CH=C~
NC -~ CN (C) CH - ~ H
3 ( 2)3 CH3 and the procedure is otherwise as described in Example 1, yellow-coloured mouldings with good lightfastness are obtained.
Le A 34 197-Foreign Countries Example 10 to 15 The following dyes may be used instead of the dye;s of the formulae A, B and C
in Examples 1 to 9, with similar substances:
NC ~ -Butyl i -Butvyi CN
10 NC~C-CH / \ N-(CH2)2 N ~ ~ CH=C~
CN
_ ~ H2CHs ~ HZCHs NC'C-CH ~ ~ N-(CH2)2 N ~ ~ CH-C~ N
NCB i -Butyl i -ESutyl RCN
12 CHsCH202C''C_CH ~ \ N-(CH2)z N- ~ ~ CH=C~C02CH2CH3 13 NC~C-CH ~ ~ N-(CH2)4 N--~ ~ ~ CH=C~ N
CN
NCB i H2CH3 ~ H2CH3 CN
14 NC'C-CH ~ ~ N-CH2CH2 O-CH2CH2 N ~ \ CH=C~CN
Le A 34 197-Foreign Countries NCB j H2 ( RCN
15 NC~C-CH / \ N-(CH2)2 N ~ ~ CH=C~
CN
Process for bulk dyeing of plastics The invention relates to a process for bulk dyeing of plastics, characterized in that use is made of dyes of the formula (I) R2 R2.
NC - ~ ~ R4 R4' ~ ~ CH=C/CN
R1 C-CH N-Y-N ~ ~R~~ (I) R3 R3, where Y is a bivalent radical selected from the group consisting of substituted and unsubstituted arylenes and alkylenes, where the alkylene radicals may, if desired, have interruption by heteroatoms, such as O or S, Rl and R1', independently of one another, are an electron-withdrawing group, preferably cyano or alkoxycarbonyl, in particular C1-C4-alkoxycarbonyl, R2, R2', R3 and R3', independently of one another <~re hydrogen, alkyl, in particular Cl-C4-alkyl, CF3 or halogen, preferably F or Cl, R4 and R4', independently of one another, are un.substituted or substituted alkyl, preferably C1-C6-alkyl, or C~-C12-aralkyl, preferably benzyl.
In one preferred embodiment, Y represents unsubstituted or substituted phenylene, or unsubstituted or substituted C1-C6-alkylene, and examples of particularly preferred radicals Y
are: 1,3-phenylene, 1,4-phenylene or methyl-substituted 1,3- or 1,4-phenylene, ~-CH2-CH2-, -CH2CH2CH2-, -(CH2)4-, -CH2CH(CH3)-, -CH2CH2-O-CH2CH2- and -CH2CH2-S-CH2;CH2-.
Le A 34 197-Foreign Countries Very particular preference is given to alkylene radicals, in particular -t:H2CH2-, -(CH2)3-, -(CH2)4-, and -CH2CH2-O-CH2CH2-.
Examples of preferred radicals Rl and Rl' are: -CN, -C02CH3, -C02CH2CH3, -CO2(CH2)2CH3 and -C02(CHZ)3CH3.
Examples of preferred radicals R2, R2', R3 and R3' axe hydrogen, methyl, ethyl, Cl, F, CF3, methoxy and ethoxy.
Examples of preferred radicals R4 and R4' are CH3, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
In one preferred embodiment, R1 = R1', R2 = R2', R3 = R3' and R4 = R4' in formula (I) in the use according to the invention.
It is particularly preferable to use dyes of the formula (Ia) Rz R2 NC C-CH ~ \ N-Y-N ~ \~-CH=C~
Ri ~ R1 (Ia) where Y is unsubstituted or substituted phenylene, in particular 1,3- or 1,4-phenylene, or unsubstituted or substituted C2-C6-al:kylene, in particular ethylene, propylene or butylene, ' CA 02338126 2001-02-23 Le A 34 197-Foreign Countries R1 is CN, C02CH3, C02CH2CH3 or COZ(CH2)3CH3, R2 is hydrogen, CH3 or CH2CH3, and R4 is CH3, CH2CH3, n-propyl or n-butyl.
Preference is likewise given to the use of dyes of the. formula (I) where at least one of the substituent pairs Rl/Ri~, R2/R2', R3/R3' and R'4/R4~ is non-identical (e.g.. Rl ~
Rl'). These asymmetric dyes of the formula (I) are also provided by this invention.
For the purposes of this application, bulk dyeing is in particular processes in which the dye of the formula (I) is incorporated into the molten plastic material, e.g. with the aid of an extruder, or in which the dye is added straight away to the starting materials for preparing the plastic, e.g. to the monorr~ers, prior to polymerization.
The approximate processing temperatures here are from 100 to 380°C.
Some of the dyes to be used according to the invention are known (e.g. CH-516 628, JP-A 02 292 371), and others may be prepared by analogy with processes known from the literature. An example of a preparation is a. Vilsmeier formylation followed by condensation with a reactive methylene compound, preferably malononitrile.
A preferred preparation is the condensation of a substituted aniline with a di-halogenoalkylene (Eq. 1) Le A 34 197-Foreign Countries R2 R2, Ra Ra, rt I
NH + X (CH2)n X + HN ~ ~ (Eq. 1 ) R3 R3, Rz R2 Ra Ra N-(CH2)~ N
-HX
R2 R2.
a R
NH + X-(CH2)~ IJ ~ ~ (Eq.2) R3 R3, where n is from 2 to 6, and X represents halogen, in particular Cl or Br, and the other substituents are as defined above, or condensation of a substituted aniline with an N-(halogenoalkyl)aniline (Eq.
2), for example in a solvent or in bulk, in the presence o P a base, followed by Vilsmeier formylation (preferably by reacting with POCl3 and dimethylformamide, followed by hydrolysis), followed by condensation with a :reactive methylene compound, preferably malononitrile.
Examples which may be mentioned of suitable thermoplastics are: cellulose esters, such as cellulose nitrate, cellulose acetate, cellulose triacetate, cellulose acetobutyrate Le A 34 197-Foreign Countries -S-and cellulose propionate, cellulose ethers, such as rnethylcellulose, ethylcellulose and benzylcellulose, linear saturated polyester resins;, aniline resins, polycarbonates, polystyrene, polyvinylcarbazole, polyvinyl chloride, in particular unplasticized PVC, polymethacrylates, polyvinylidene chloride, polya~crylonitrile, polyoxymethylenes, linear polyurethanes, and also copolymers, such as vinyl chloride-vinyl acetate copolymers, and also in particular styrene copolymers, such as styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers (SB) and styrene-oc-methylstyrene copolymers (SMS) and acrylonitrile-butadiene-styrene copolymers (ABS).
The high-molecular-weight compounds mentioned may be present individually or in mixtures, as plastic materials or melts; which may be spun to give fibres, if desired.
The novel process is particularly suitable for bullk dyeing of polystyrene, and in particular for bulk dyeing of poly(meth)acrylat:es, and preferably polymethyl methacrylate SAN, SMS, ABS, or else polyethylene terephthalate or polybutylene terephthalate.
It is expedient for the plastics to be dyed to be in the form of powders, chips or pellets and to be mixed intimately with the dye. One method of achieving this is by coating the plastic particles with the finely divided dry pulverulent dye, or by treating the particles with a solution or dispersion of the dye in an organic solvent and then removing the solvent.
The process of the invention may also use mixtures of different dyes of the formula (I) and/or mixtures of dyes of the formula (I) with other dyes and/or with inorganic or organic pigments.
The dyes of the formula (I) are preferably in their solid form, in particular pulverulent or granular, when used according to the invention.
Le A 34 197-Foreign Countries S
These solid dye preparations comprise at least 95~% by weight, preferably at least 98% by weight, in particular more than 99% by wei~;ht, of dye of the formula (I) and, if desired, up to 5% by weight of organic binder, in each case based on the dye preparation.
These dye preparations are also provided by the invention.
Examples of possible binders are ethylene oxide-propylene oxide block copolymers, preferably those with a molar mass of from 4000 to L 6,000 g/mol.
When used for dyeing, the dye preparations are in particular preferably in the form of powders, in particular in the form of dry powders which have been ground and screened, or else are in the form of pellets, such as those which may be prepared in accordance with EP-A-488 933, for example.
The ratio of dye to plastic can vary within wide limits, depending on the desired colour strength. It is generally advisable to use from 0.005 to 5% by weight, preferably from 0.01 to 2% by weight, of dye, based on the amount of the plastic to be dyed.
Corresponding high-quality opaque colourings can be obtained by adding pigments insoluble in the polymers, e.g. titanium dioxide.
Examples of the amounts of titanium dioxide which can be used are from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the amount of polymer.
The treated polymer particles are melted by known processes in an extruder and extruded to give articles such as films or fibres, or cast to give sheets.
Le A 34 197-Foreign Countries _7_ One way of dyeing the plastics with the dyes of thc~ formula (I) is to admix a dye of this type, if desired in the form of a masterbatch, with these substrates using roll mills, mixing equipment or grinding equipment. T'he dyed material is then brought into its desired final form by processes known per se, such as calandering, S compression moulding, extruding, spreading, casting or inj ection moulding.
It is often desirable to incorporate what are known as plasticizers into the high-molecular-weight compounds prior to shaping, in order to produce non-rigid mouldings or to reduce the brittleness of the same. Examples of the plasticizers which can be used are esters of phosphoric acid, ph.thalic acid or sebacic acid. In the process of the invention, the plasticizers may be iincorporated prior to or after the incorporation of the dye into the polymers. It is rr~oreover possible for any desired amounts of fillers and/or other colouring constituents, such as white pigments, colour pigments or black pigments, to be added alongside the compounds of the formula (I) to the high-molecular-weight organic substances in order to achieve different shades.
The resultant greenish-to reddish-yellow colourings have good light resistance and good weathering resistance. The dyes of the invention are also very heat-fast within the thermoplastics.
Le A 34 197-Foreign Countries _g_ Example 1 0.1 g of the dye of the formula CH3 i H3 NC CHZ CH2 , CN
C=CH / \ N-CH2 CHZ N ~ \ CH=C~
NC CN (A) and 2 g of titanium dioxide (Bayertitan~ R-FK-2), and 100 g of a pelletized polystyrene are mixed for 2 hours in a sealed container on a roller bed. The resultant mixture is extruded at about 230°C to extrudates of width 2 cm and repelletized. The pellets are injection moulded at from 230 to 240°C. This gives reddish-yellow-coloured mouldings with high light resistance and high brilliance.
Example 2 0.02 g of the dye of the formula (A) and 100 g of a :pelletized polystyrene are mixed for 2 hours in a sealed container on a roller bed. The resultant mixture is then injection moulded at from 230°C to 240°C, using an injection-moulding machine with a screw, to give mouldings. The yellow-coloured, transparent mouldings have high lightfastness.
Example 3 If the dye of the formula (I) is replaced by the dye of the formula (B) ' CA 02338126 2001-02-23 Le A 34 197-Foreign Countries NC ~ ~ ~ ~ ,CN
C=CH N (CH2)4 N CH=C~
NC CN
CH3 CH3 (B) and the procedure is otherwise as described in Example 1, yellow-coloured mouldings with high lightfastness are obtained.
S
Example 4 If 0.035 g of the dye of the formula (B) and 100 ;g of a pelletized polystyrene are mixed and the procedure is otherwise as described in Example 2, yellow-coloured, transparent mouldings with high lightfastness are obtained.
Example 5 0.03 g of dye of the formula (A) are dissolved in '99.97 g of methyl metr~acrylate.
After addition of 0.01 g of dibenzoyl peroxide the solution is heated to 120°C and the polymerization initiated. After 30 minutes, the methyl methacrylate which has begun to polymerize is placed between two glass plates and the polymerization completed for 10 hours at 80°C. This gives yellow-colouref., transparent polymethyl meth-acrylate sheets.
Example 6 0.02 g of dye of the formula (B) and 100 g of polymethyl methacrylate are mixed dry and homogenized in a twin-screw extruder at 240°C. The material discharged as extrudate is pelletized. It is then shaped by press-moulding. This gives a transparent, yellow-coloured plastic with very good lightfastness and weather fastness.
Le A 34 197-Foreign Countries Example 7 100 g of a commercially available polycarbonate in the form of pellets are mixed dry with 0.01 g of solid of the formula (A). The resull:ant pellets are homogenized in a twin-screw extruder at 350°C. This gives a transparent, yellow coloration with good lightfastness. The dyed polycarbonate is discharged as extrudate and pelietized. The pellets may be processed by customary thermoplastic processing methods.
Example 8 0.04 g of solid of the formula (B) are mixed dry with 100 g of styrene-acrylonitrile copolymer and homogenized in a twin-screw extruder at 190°C and pelletized, and may then be shaped in the usual way by press-moulding. This gives a transparent, coloured plastic with good lightfastness. If 1% of titanium dioxide is added during the operation an opaque coloration is obtained.
Example 9 If in Example 1 the dye of the formula (A) is replace-d by the dye of the formula (CH2)3 CH3 NC / ' ~~ ,CN
C=CH N-CH2 CH2 N ~ CH=C~
NC -~ CN (C) CH - ~ H
3 ( 2)3 CH3 and the procedure is otherwise as described in Example 1, yellow-coloured mouldings with good lightfastness are obtained.
Le A 34 197-Foreign Countries Example 10 to 15 The following dyes may be used instead of the dye;s of the formulae A, B and C
in Examples 1 to 9, with similar substances:
NC ~ -Butyl i -Butvyi CN
10 NC~C-CH / \ N-(CH2)2 N ~ ~ CH=C~
CN
_ ~ H2CHs ~ HZCHs NC'C-CH ~ ~ N-(CH2)2 N ~ ~ CH-C~ N
NCB i -Butyl i -ESutyl RCN
12 CHsCH202C''C_CH ~ \ N-(CH2)z N- ~ ~ CH=C~C02CH2CH3 13 NC~C-CH ~ ~ N-(CH2)4 N--~ ~ ~ CH=C~ N
CN
NCB i H2CH3 ~ H2CH3 CN
14 NC'C-CH ~ ~ N-CH2CH2 O-CH2CH2 N ~ \ CH=C~CN
Le A 34 197-Foreign Countries NCB j H2 ( RCN
15 NC~C-CH / \ N-(CH2)2 N ~ ~ CH=C~
CN
Claims (14)
1. Process for bulk dyeing of plastics, characterized in that use is made of dyes of the formula (I) where Y is a bivalent radical selected from the group consisting of substituted and unsubstituted arylenes and alkylenes, where the alkylene radicals may, if desired, have interruption by heteroatoms, such as O or S, R1 and R1', independently of one another, are an electron-withdrawing group, preferably cyano or alkoxycarbonyl, in particular C1-C4-alkoxy-carbonyl, R2, R2', R3 and R3', independently of one another are hydrogen, alkyl, in particular C1-C4-alkyl, CF3 or halogen, preferably F or Cl, R4 and R4', independently of one another, are unsubstituted or substituted alkyl, preferably C1-C6-alkyl, or C7-C12-aralkyl, preferably benzyl.
2. Process according to Claim 1, characterized in that Y represents unsubstituted or substituted phenylene, in particular 1,3-phenylene, 1,4-phenylene or methyl-substituted 1,3- or 1,4-phenylene, or unsubstituted or substituted C2-C6-alkylene, in particular -CH2-CH2-, -CH2CH2CH2-, -(CH2)4-, -CH2CH(CH3)-, -CH2CH2OCH2CH2- or -CH2CH-S-CH2CH2-.
3. Process according to Claim 1, characterized in that R1 and R1', independently of one another, are CN, CO2CH3, CO2CH2CH3, -CO2(CH2)2CH3 or CO2(CH2)3CH3.
4. Process according to Claim 1, characterized in that the radicals R2, R2', and R3', independently of one another, are hydrogen, methyl, ethyl, Cl, F or CF3.
5. Process according to Claim 1, characterized in that the radicals R4 arid R4' are CH3, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
6. Process according to Claim 1, characterized in that R1 = R1', R2 = R2', R3 =
R3' and R4 = R4'.
R3' and R4 = R4'.
7. Process according to Claim 1, characterized in that use is made of dyes of the formula (Ia) where Y is unsubstituted or substituted phenylene, in particular 1,3- or 1,4-phenylene, or unsubstituted or substituted C2-C6-alkylene, in particular ethylene, propylene or butylene, R1 is CN, CO2CH3, CO2CH2CH3 or CO2(CH2)3CH3, R2 is hydrogen, CH3 or CH2CH3, and R4 is CH3, CH2CH3, n-propyl or n-butyl.
8. Process according to Claim 1, characterized in that use is made of dyes of the formula (I) where at least one of the substituent pairs R1/R1', R2/R2', R3/R3' and/or R4/R4' is non-identical.
9. Process according to Claim 1, characterized in that use is made of at least one dye selected from the group below:
10. Compounds of the formula where Y is a bivalent radical selected from the group consisting of substituted and unsubstituted arylenes and alkylenes, where the alkylene radicals may, if desired, have interruption by heteroatoms, such as O or S, R1 and R1', independently of one another, are an electron-withdrawing group, preferably cyano or alkoxycarbonyl, in particular C1-C4-alkoxy-carbonyl, R2, R2', R3 and R3', independently of one another are hydrogen, alkyl, in particular C1-C4-alkyl, CF3 or halogen, preferably F or Cl, R4 and R4', independently of one another, are unsubstituted or substituted alkyl, preferably C1-C6-alkyl, or C7-C12-aralkyl, preferably benzyl, and where at least one of the substituent pairs R1/R1', R2/R2', R3/R.3' and/or R4/R4' is non-identical.
11. Solid dye preparations comprising at least 95% by weight of a dye of the formula (I) according to Claim 1.
12. Process for preparing dyes according to Claim 10, characterized in that a substituted aniline is reacted with a dihalogenoalkylene where n is from 2 to 6, X is halogen, in particular Br or Cl, and the other substituents are as defined above, or a substituted aniline is reacted with an N-(halogenoalkyl)aniline (Eq. 2), for example in a solvent or in bulk in the presence of a base, followed by a Vilsmeier formylation (preferably by reacting with POCl3 and dimethyl-formamide, followed by hydrolysis) followed by condensation with a reactive methylene compound, preferably malononitrile.
13. Plastics dyed with at least one dye according to Claim 10.
14. Copolymer from the group consisting of styrene-acrylonitrile copolymers (SAN) and acrylonitrile-butadiene-styrene copolymers (ABS), dyed with at least one dye of the formula (I) according to Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10009580.1 | 2000-02-29 | ||
| DE10009580A DE10009580A1 (en) | 2000-02-29 | 2000-02-29 | Process for mass coloring plastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2338126A1 true CA2338126A1 (en) | 2001-08-29 |
Family
ID=7632861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002338126A Abandoned CA2338126A1 (en) | 2000-02-29 | 2001-02-23 | Process for bulk dyeing of plastics |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20010020313A1 (en) |
| EP (1) | EP1130052A3 (en) |
| JP (1) | JP2001288274A (en) |
| KR (1) | KR20010085655A (en) |
| CN (1) | CN1311267A (en) |
| CA (1) | CA2338126A1 (en) |
| DE (1) | DE10009580A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10201760A1 (en) * | 2002-01-18 | 2003-07-31 | Bayer Ag | Process for the preparation of styryl compounds |
| CN108623825B (en) * | 2018-05-18 | 2021-07-09 | 海南热带海洋学院 | Marine pollution microplastic dyeing method |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3553245A (en) * | 1964-10-19 | 1971-01-05 | Eastman Kodak Co | Cyanomethylidene aniline compounds |
| CH516628A (en) * | 1967-08-08 | 1971-12-15 | Ciba Geigy Ag | Bistyryl dyestuff prepn - contg water-insol dyestuff, for dyeing polyesters greenish-yellow |
| DE2446759C2 (en) * | 1974-10-01 | 1982-12-02 | Bayer Ag, 5090 Leverkusen | Styryl dyes |
| DE2447229A1 (en) * | 1974-10-03 | 1976-04-15 | Bayer Ag | STYRIC DYES |
| US4331584A (en) * | 1979-06-04 | 1982-05-25 | Sumitomo Chemical Company, Limited | Styryl compounds and coloring synthetic resins therewith |
| JPS6018700B2 (en) * | 1980-04-28 | 1985-05-11 | 住友化学工業株式会社 | Styryl compounds, their production methods, and methods for coloring polymeric organic materials using them |
| US5218136A (en) * | 1987-12-28 | 1993-06-08 | Sumitomo Chemical Company, Limited | Styryl compounds, process for preparing the same and photoresist compositions comprising the same |
| US5223476A (en) * | 1989-05-02 | 1993-06-29 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
| JPH02292371A (en) * | 1989-05-02 | 1990-12-03 | Sankyo Kagaku Kk | Coloring matter for thermal transfer recording |
| US5106942A (en) * | 1990-01-08 | 1992-04-21 | Eastman Kodak Company | Copolymerized methine colorant-polyester color concentrates |
| DE4004614A1 (en) * | 1990-02-15 | 1991-08-22 | Basf Ag | METHOD FOR TRANSMITTING METHINE DYES CONTAINING BICHROMOPHORES IN CYANOGROUPES |
-
2000
- 2000-02-29 DE DE10009580A patent/DE10009580A1/en not_active Withdrawn
-
2001
- 2001-02-16 EP EP01103520A patent/EP1130052A3/en not_active Withdrawn
- 2001-02-20 US US09/789,367 patent/US20010020313A1/en not_active Abandoned
- 2001-02-23 CA CA002338126A patent/CA2338126A1/en not_active Abandoned
- 2001-02-26 JP JP2001050173A patent/JP2001288274A/en active Pending
- 2001-02-27 KR KR1020010009925A patent/KR20010085655A/en not_active Withdrawn
- 2001-02-28 CN CN01108951A patent/CN1311267A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1130052A2 (en) | 2001-09-05 |
| US20010020313A1 (en) | 2001-09-13 |
| EP1130052A3 (en) | 2003-11-12 |
| DE10009580A1 (en) | 2001-08-30 |
| JP2001288274A (en) | 2001-10-16 |
| KR20010085655A (en) | 2001-09-07 |
| CN1311267A (en) | 2001-09-05 |
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