WO2003033584A2 - A method of producing coloured plastics or coloured polymeric particles - Google Patents

A method of producing coloured plastics or coloured polymeric particles Download PDF

Info

Publication number
WO2003033584A2
WO2003033584A2 PCT/EP2002/011167 EP0211167W WO03033584A2 WO 2003033584 A2 WO2003033584 A2 WO 2003033584A2 EP 0211167 W EP0211167 W EP 0211167W WO 03033584 A2 WO03033584 A2 WO 03033584A2
Authority
WO
WIPO (PCT)
Prior art keywords
formula
dye
absorber
coloured
plastics
Prior art date
Application number
PCT/EP2002/011167
Other languages
French (fr)
Other versions
WO2003033584A3 (en
Inventor
Ian Christensen
Marie-Raphael Morvillier
Original Assignee
Ciba Specialty Chemicals Holding Inc.
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4566638&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2003033584(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to US10/492,182 priority Critical patent/US7193001B2/en
Priority to JP2003536320A priority patent/JP4312601B2/en
Priority to EP02779464A priority patent/EP1434818B1/en
Priority to BR0213174-9A priority patent/BR0213174A/en
Priority to MXPA04002043A priority patent/MXPA04002043A/en
Priority to CA002457247A priority patent/CA2457247A1/en
Priority to DE60229153T priority patent/DE60229153D1/en
Publication of WO2003033584A2 publication Critical patent/WO2003033584A2/en
Publication of WO2003033584A3 publication Critical patent/WO2003033584A3/en
Priority to US11/702,730 priority patent/US20070130704A1/en

Links

Classifications

    • 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
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • 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

Definitions

  • the present invention relates to a method of producing coloured plastics or coloured polymeric particles.
  • Dyes and the use thereof for colouring plastics and polymeric particles are known.
  • the use of the known dyes on their own for colouring plastics in the mass has not, however, always fully met the increased demands, especially in terms of light fastness properties.
  • There is accordingly a need for new colouring methods for the production of colourations in the mass that have a high tinctorial strength and, especially, light fastness and high temperature light fastness, and that exhibit good all-round fastness properties.
  • the present invention accordingly relates to a method of producing coloured plastics or coloured polymeric particles that comprises using a dye of formula
  • R . is a radical of formula
  • R 2 is hydrogen or C C 4 alkyl
  • R 3 is hydrogen or d-C ⁇ alkyl, and/or a dye of formula
  • R 2 and R 3 as C dalkyl are each independently of the other methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
  • R 2 is preferably ethyl.
  • R 3 is preferably methyl.
  • the amounts in which the dyes are admixed with the plastics or polymeric particles to be coloured can vary within wide limits depending on the desired depth of shade; generally, amounts of from 0.001 to 5 % by weight, especially from 0.01 to 2 % by weight, more especially from 0.03 to 0.5 % by weight, based on the material to be coloured, have proved advantageous.
  • UV absorbers suitable for the method according to the invention include especially 2-(2'-hyd- roxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of substituted or unsubstituted benzoic acid, acrylates, oxamides, 2-(2-hydroxyphenyl)-1 ,3,5-triazines, monobenzoates of resorcinol and formamidines, and also a polyester UV absorber of formula
  • 2-(2'-hydroxyphenyl)benzotriazoles From the class of the 2-(2'-hydroxyphenyl)benzotriazoles the following, for example, may be mentioned: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(5'-tert-butyl-2 , -hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1,3,3- tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzo- triazole, 2-(3'-tert-butyl-2 , -hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'- tert-but
  • R 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-( , ⁇ - dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]benzotriazole; and 2-[2'-hydroxy-3'- (1,1 ,3,3-tetramethylbutyl)-5'-( , ⁇ -dimethylbenzyl)phenyl]benzotriazole.
  • 2-hydroxybenzophenones From the class of the 2-hydroxybenzophenones the following, for example, may be mentioned: 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-tri- hydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • 2-(2-hydroxyphenyl)-1 ,3,5-triazines From the class of the 2-(2-hydroxyphenyl)-1 ,3,5-triazines the following, for example, may be mentioned: 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxy- phenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dime- thylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1 ,3,5-triazine, 2-(
  • oxamides From the class of the oxamides the following, for example, may be mentioned: 4,4'-dioctyl- oxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyl- oxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)ox- amide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-2'-ethyl- 5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-
  • esters of substituted or unsubstituted benzoic acid the following, for example, may be mentioned: 4-tert-butyl-phenyl salicylate, phenyl salicylates, octylphenyl salicylates, diben- zoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octade- cyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl- 4-hydroxybenzoate.
  • ethyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate isooctyl- ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl- ⁇ -carbomethoxycinna- mate, methyl- -cyano- ⁇ -methyl-p-methoxycinnamate, butyl- ⁇ -cyano- ⁇ -methyl-p-methoxy- cinnamate, methyl- ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbomethoxy- ⁇ -cyano- vinyl)-2-methylindoline.
  • a monobenzoate resorcinol is, for example, a compound of formula
  • a formamidine is, for example, a compound of formula
  • compositions comprising active methine compounds, for example unsubstituted or substituted malonate esters, as described, for examp- le, in US-A-6207740, WO-A-02/14418, EP-A-0350386, US-A-4661 566, US-A-4749772 and EP-A-0272 692.
  • the amount of UV absorber can vary within a wide range; advantageously from 0.01 to 1.0 % by weight, especially from 0.02 to 0.6 % by weight, and more especially from 0.05 to 0.4 % by weight, of a UV absorber based on the weight of the plastics or polymeric particles is used.
  • the compounds of formulae (1) to (9) are known and can be prepared in a manner known per se according to known methods.
  • the method according to the invention of producing coloured plastics or coloured polymeric particles is carried out, for example, by admixing with those substrates, using roll mills or mixing or grinding apparatuses, at least one dye of formula (1 ) and/or the dye of formula (4) and a UV absorber, the dye and the UV absorber being dissolved or finely distributed in the high molecular weight material.
  • the dye and UV absorber can be added simultaneously or in succession, it being possible for the order in which they are added to be selected as desired.
  • the dyes of formulae (1) and (4) can be used either alone or, preferably, in combination with other dyes.
  • the high molecular weight organic material with the admixed dye and UV absorber is then processed according to methods known perse, such as, for example, calendering, compression moulding, extrusion, coating, spinning, pouring or injection moulding, as a result of which the coloured material acquires its final shape.
  • Admixture of the dye and the UV absorber can also be effected directly before the actual processing step, for example by continuously metering, directly into the inlet zone of an extruder, a pulverulent dye, a pulverulent UV absorber and a granulated or pulverulent high molecular weight organic material and, optionally, also other ingredients, such as additives, the constituents being mixed in just before being processed.
  • plasticisers In order to produce non-rigid mouldings or to reduce brittleness, it is frequently 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 can be incorporated into the polymers before or after the incorporation of the dye. It is also possible, in order to achieve different colour shades, to add to the high molecular weight organic materials, in addition to a dye of formula (I) and/or the dye of formula (4), also further dyes or also other colourants in any desired amounts, optionally together with further ingredients, e.g. fillers or siccatives.
  • thermoplastic plastics especially in the form of granules or mouldings, such as, for example, containers for solid or liquid substances, for example bottles, especially containers and bottles for drinks, especially beer.
  • Preferred high molecular weight organic materials that can be coloured in accordance with the invention are generally polymers having a dielectric constant > 2.5, especially polyesters, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, sty- rene/acrylonitrile (SAN) and acrylonitrile/butadiene/styrene (ABS).
  • polyesters and polyamide More especially preferred are linear aromatic polyesters, which can be obtained by polycondensation of terephthalic acid and gly- cols, especially ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hy- droxymethyl)cyc!ohexane, for example polyethylene terephthalate (PET) or polybutylene te- rephthalate (PBTP); also polycarbonates, e.g. those from ⁇ , ⁇ -dimethyl-4,4-dihydroxy-diphe- nylmethane and phosgene, or polymers based on polyvinyl chloride and also on polyamide, for example polyamide 6 or polyamide 6.6.
  • PET polyethylene terephthalate
  • PBTP polybutylene te- rephthalate
  • polycarbonates e.g. those from ⁇ , ⁇ -dimethyl-4,4-dihydroxy-diphe- nylmethane and pho
  • the dyes of formula (1) and (4) are used to colour beer bottles made of polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the materials mentioned hereinabove, especially those of polyesters, that have been coloured using the method according to the invention are distinguished by level and tinctorially strong colour shades having very good in-use fastness properties, especially a good light fastness and high temperature light fastness.
  • the invention relates also to the use of a combination of a dye of formula (1 ) and/or the dye of formula (4) and a UV absorber for colouring plastics or polymeric particles.
  • the invention relates furthermore to the plastics coloured in the mass by the methods mentioned hereinabove.
  • the following Examples serve to illustrate the invention. Unless specified otherwise, 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 between grams and cubic centimetres.
  • polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
  • the homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6 heating zones, and is cooled with water, granulated in a Marke Sheer granulator and then dried for 4 hours at 130°C in a drier (Turb Etuve TE 25, MAPAG AG, CH-3001 Bern).
  • polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
  • the homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6 heating zones, and is cooled with water, granulated in a Marke Sheer granulator and then dried for 4 hours at 130°C in a drier (Turb Etuve TE 25, MAPAG AG, CH-3001 Bern).
  • polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
  • the homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention relates to a method of producing coloured plastics or coloured polymeric particles which comprises using a dye of formula (1), wherein R1 is a radical of formula (2) or of formula (3), wherein R2 is hydrogen or C1-C4alkyl, and R3 is hydrogen or C1-C4alkyl, and/or a dye of formula (4) and a UV absorber.

Description

A method of producing coloured plastics or coloured polymeric particles
The present invention relates to a method of producing coloured plastics or coloured polymeric particles.
Dyes and the use thereof for colouring plastics and polymeric particles are known. The use of the known dyes on their own for colouring plastics in the mass has not, however, always fully met the increased demands, especially in terms of light fastness properties. There is accordingly a need for new colouring methods for the production of colourations in the mass that have a high tinctorial strength and, especially, light fastness and high temperature light fastness, and that exhibit good all-round fastness properties.
It has now, surprisingly, been found that the method according to the invention substantially meets the above criteria.
The present invention accordingly relates to a method of producing coloured plastics or coloured polymeric particles that comprises using a dye of formula
Figure imgf000003_0001
wherein
R. is a radical of formula
Figure imgf000003_0002
or of formula
Figure imgf000003_0003
wherein
R2 is hydrogen or C C4alkyl, and R3 is hydrogen or d-C^alkyl, and/or a dye of formula
Figure imgf000004_0001
and a UV absorber.
R2 and R3 as C dalkyl are each independently of the other methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
R2 is preferably ethyl. R3 is preferably methyl.
For the method according to the invention, preference is given to the dyes of formulae (4),
Figure imgf000004_0002
and
Figure imgf000005_0001
The amounts in which the dyes are admixed with the plastics or polymeric particles to be coloured can vary within wide limits depending on the desired depth of shade; generally, amounts of from 0.001 to 5 % by weight, especially from 0.01 to 2 % by weight, more especially from 0.03 to 0.5 % by weight, based on the material to be coloured, have proved advantageous.
UV absorbers suitable for the method according to the invention include especially 2-(2'-hyd- roxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of substituted or unsubstituted benzoic acid, acrylates, oxamides, 2-(2-hydroxyphenyl)-1 ,3,5-triazines, monobenzoates of resorcinol and formamidines, and also a polyester UV absorber of formula
Figure imgf000005_0002
having a specific weight of from 1200 to 1400, preferably from 1300 to 1350, at 25°C.
From the class of the 2-(2'-hydroxyphenyl)benzotriazoles the following, for example, may be mentioned: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(5'-tert-butyl-2,-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1,3,3- tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzo- triazole, 2-(3'-tert-butyl-2,-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'- tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hy- droxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5- chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5- chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro- benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'- [2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy- 5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-iso-octyloxycarbonylethyl)phe- nylbenzotriazole, 2,2'-methylene-bis[4-(1 ,1 ,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the product of the esterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphe-
nyl]-2H-benzotriazole with polyethylene glycol 300; [R - CH2CH2 - COO- CH2CH2-] — ,
wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-( ,α- dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]benzotriazole; and 2-[2'-hydroxy-3'- (1,1 ,3,3-tetramethylbutyl)-5'-( ,α-dimethylbenzyl)phenyl]benzotriazole.
From the class of the 2-hydroxybenzophenones the following, for example, may be mentioned: 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-tri- hydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
From the class of the 2-(2-hydroxyphenyl)-1 ,3,5-triazines the following, for example, may be mentioned: 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxy- phenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dime- thylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy- 4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxy- phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypro- pyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyl- oxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hy- droxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2- hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6- diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1 ,3,5-triazine and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-triazine. From the class of the oxamides the following, for example, may be mentioned: 4,4'-dioctyl- oxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyl- oxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)ox- amide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-2'-ethyl- 5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
As esters of substituted or unsubstituted benzoic acid the following, for example, may be mentioned: 4-tert-butyl-phenyl salicylate, phenyl salicylates, octylphenyl salicylates, diben- zoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octade- cyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl- 4-hydroxybenzoate.
From the class of the acrylates the following, for example, may be mentioned: ethyl-α-cyano- β,β-diphenyl acrylate, isooctyl-α-cyano-β,β-diphenyl acrylate, methyl-α-carbomethoxycinna- mate, methyl- -cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxy- cinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyano- vinyl)-2-methylindoline.
A monobenzoate resorcinol is, for example, a compound of formula
Figure imgf000007_0001
A formamidine is, for example, a compound of formula
Figure imgf000007_0002
As UV absorbers it is also possible to use compositions comprising active methine compounds, for example unsubstituted or substituted malonate esters, as described, for examp- le, in US-A-6207740, WO-A-02/14418, EP-A-0350386, US-A-4661 566, US-A-4749772 and EP-A-0272 692.
The amount of UV absorber can vary within a wide range; advantageously from 0.01 to 1.0 % by weight, especially from 0.02 to 0.6 % by weight, and more especially from 0.05 to 0.4 % by weight, of a UV absorber based on the weight of the plastics or polymeric particles is used.
The compounds of formulae (1) to (9) are known and can be prepared in a manner known per se according to known methods.
The method according to the invention of producing coloured plastics or coloured polymeric particles is carried out, for example, by admixing with those substrates, using roll mills or mixing or grinding apparatuses, at least one dye of formula (1 ) and/or the dye of formula (4) and a UV absorber, the dye and the UV absorber being dissolved or finely distributed in the high molecular weight material. The dye and UV absorber can be added simultaneously or in succession, it being possible for the order in which they are added to be selected as desired.
The dyes of formulae (1) and (4) can be used either alone or, preferably, in combination with other dyes.
Preference is given to a combination of the dye of formula (4), the dye of formula
Figure imgf000008_0001
and the dye of formula
Figure imgf000009_0001
Preference is given likewise to a combination of the dye of formula (4), the dye of formula (5), the dye of formula (10) and the dye of formula (11).
Preference is given likewise to a combination of the dye of formula (4), the dye of'formula (6), the dye of formula (10) and the dye of formula (11).
The high molecular weight organic material with the admixed dye and UV absorber is then processed according to methods known perse, such as, for example, calendering, compression moulding, extrusion, coating, spinning, pouring or injection moulding, as a result of which the coloured material acquires its final shape.
Admixture of the dye and the UV absorber can also be effected directly before the actual processing step, for example by continuously metering, directly into the inlet zone of an extruder, a pulverulent dye, a pulverulent UV absorber and a granulated or pulverulent high molecular weight organic material and, optionally, also other ingredients, such as additives, the constituents being mixed in just before being processed. Generally, however, preference is given to mixing the dye and the UV absorber into the high molecular weight organic material prior to processing, since more uniformly coloured substrates can be obtained.
In order to produce non-rigid mouldings or to reduce brittleness, it is frequently 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 can be incorporated into the polymers before or after the incorporation of the dye. It is also possible, in order to achieve different colour shades, to add to the high molecular weight organic materials, in addition to a dye of formula (I) and/or the dye of formula (4), also further dyes or also other colourants in any desired amounts, optionally together with further ingredients, e.g. fillers or siccatives.
Preference is given to the colouring of thermoplastic plastics, especially in the form of granules or mouldings, such as, for example, containers for solid or liquid substances, for example bottles, especially containers and bottles for drinks, especially beer. Preferred high molecular weight organic materials that can be coloured in accordance with the invention are generally polymers having a dielectric constant > 2.5, especially polyesters, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, sty- rene/acrylonitrile (SAN) and acrylonitrile/butadiene/styrene (ABS).
Especially preferred are polyesters and polyamide. More especially preferred are linear aromatic polyesters, which can be obtained by polycondensation of terephthalic acid and gly- cols, especially ethylene glycol, or condensation products of terephthalic acid and 1 ,4-bis(hy- droxymethyl)cyc!ohexane, for example polyethylene terephthalate (PET) or polybutylene te- rephthalate (PBTP); also polycarbonates, e.g. those from α,α-dimethyl-4,4-dihydroxy-diphe- nylmethane and phosgene, or polymers based on polyvinyl chloride and also on polyamide, for example polyamide 6 or polyamide 6.6.
Preferably, the dyes of formula (1) and (4) are used to colour beer bottles made of polyethylene terephthalate (PET).
The materials mentioned hereinabove, especially those of polyesters, that have been coloured using the method according to the invention are distinguished by level and tinctorially strong colour shades having very good in-use fastness properties, especially a good light fastness and high temperature light fastness.
The invention relates also to the use of a combination of a dye of formula (1 ) and/or the dye of formula (4) and a UV absorber for colouring plastics or polymeric particles. The invention relates furthermore to the plastics coloured in the mass by the methods mentioned hereinabove. The following Examples serve to illustrate the invention. Unless specified otherwise, 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 between grams and cubic centimetres.
Example 1 :
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
130°C and then homogeneously mixed in a roller rack mixing apparatus for 15 minutes, at
60 revs/min., with
0.50 g of the azo dye of formula (5) and
3.00 g of a UV absorber of formula
Figure imgf000011_0001
The homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6 heating zones, and is cooled with water, granulated in a Marke Sheer granulator and then dried for 4 hours at 130°C in a drier (Turb Etuve TE 25, MAPAG AG, CH-3001 Bern).
Yellow-coloured polyester granules having good all-round fastness properties, especially very good light fastness and high temperature light fastness, are obtained.
Example 2:
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
130°C and then homogeneously mixed in a roller rack mixing apparatus for 15 minutes, at
60 revs/min., with
0.45 g of the dye of formula (6) and
0.28 g of the UV absorber of formula (12).
The homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder (25 mm twin screw, Collin, D-85560 Ebersberg) having 6 heating zones, and is cooled with water, granulated in a Marke Sheer granulator and then dried for 4 hours at 130°C in a drier (Turb Etuve TE 25, MAPAG AG, CH-3001 Bern).
Yellow-coloured polyester granules having good all-round fastness properties, especially very good light fastness and high temperature light fastness, are obtained.
Example 3:
1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predried for 4 hours at
130°C and then homogeneously mixed in a roller rack mixing apparatus for 15 minutes, at
60 revs/min., with
0.30 g of the dye of formula (4)
0.24 g of the dye of formula (10),
0.30 g of the dye of formula (11 ) and
1.8 g of the UV absorber of formula (12).
The homogeneous mixture is extruded at a maximum temperature of 275°C in an extruder
(25 mm twin screw, Collin, D-85560 Ebersberg) having 6 heating zones, and is cooled with water, granulated in a Marke Sheer granulator and then dried for 4 hours at 130°C in a drier
(Turb Etuve TE 25, MAPAG AG, CH-3001 Bern).
Green-coloured polyester granules having good all-round fastness properties, especially very good light fastness and high temperature light fastness, are obtained.

Claims

What is claimed is:
1. A method of producing coloured plastics or coloured polymeric particles, which comprises using a dye of formula
Figure imgf000013_0001
wherein
R, is a radical of formula
Figure imgf000013_0002
or of formula
Figure imgf000013_0003
wherein
R2 is hydrogen or CrC4alkyl and R3 is hydrogen or CrC4alkyl, and/or a dye of formula
Figure imgf000013_0004
and a UV absorber.
2. A method according to claim 1 , which comprises using a dye of formula
Figure imgf000014_0001
wherein
R. is a radical of formula
Figure imgf000014_0002
wherein
R2 is hydrogen or C C4alkyl and R3 is hydrogen or C C4alkyl, and a UV absorber.
3. A method according to either claim 1 or claim 2, which comprises using, as dye of formula (1), the dye of formula
Figure imgf000014_0003
4. A method according to either claim 1 or claim 2, which comprises using, as dye of formula (1), the dye of formula
Figure imgf000015_0001
5. A method according to either claim 1 or claim 2, which comprises using as UV-absorber a UV absorber from the class of the 2-(2'-hydroxyphenyl)benzotriazoles, of the 2-hydroxyben- zophenones, of the esters of substituted or unsubstituted benzoic acid, of the acrylates, of the oxamides, of the 2-(2-hydroxyphenyl)-1 ,3,5-triazines, of the monobenzoates of resorcinol or of the formamidines, or a polyester UV absorber of formula
Figure imgf000015_0002
having a specific weight of from 1200 to 1400, preferably from 1300 to 1350, at 25°C.
6. Use of a combination of a dye of formula (1) according to claim 1 and a UV absorber for colouring plastics or polymeric particles.
7. Use of a combination of a dye of formula (4) according to claim 1 and a UV absorber for colouring plastics or polymeric particles.
8. Use of a combination according to either claim 6 or claim 7 for colouring beer bottles made of polyethylene terephthalate (PET).
9. Use according to any one of claims 6 to 8, which comprises using as UV absorber a UV absorber from the class of the 2-(2'-hydroxyphenyl)benzotriazoles, of the 2-hydroxy- benzophenones, of the esters of substituted or unsubstituted benzoic acid, of the acrylates, of the oxamides, of the 2-(2-hydroxyphenyl)-1 ,3,5-triazines, of the monobenzoates of resorcinol, or of the formamidines, or a polyester UV absorber of formula
Figure imgf000016_0001
having a specific weight of from 1200 to 1400, preferably from 1300 to 1350, at 25°C.
10. Plastics or polymeric particles coloured by a combination according to either claim 6 or claim 7.
11. Beer bottles made of polyethylene terephthalate (PET) coloured by a combination according to either claim 6 or claim 7.
PCT/EP2002/011167 2001-10-12 2002-10-04 A method of producing coloured plastics or coloured polymeric particles WO2003033584A2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US10/492,182 US7193001B2 (en) 2001-10-12 2002-10-04 Method of producing mass colored beer bottles
JP2003536320A JP4312601B2 (en) 2001-10-12 2002-10-04 Method for producing colored plastic or colored polymer particles
EP02779464A EP1434818B1 (en) 2001-10-12 2002-10-04 A method of producing coloured plastics or coloured polymeric particles
BR0213174-9A BR0213174A (en) 2001-10-12 2002-10-04 Production method of colored plastics or colored polymer particles
MXPA04002043A MXPA04002043A (en) 2001-10-12 2002-10-04 A method of producing coloured plastics or coloured polymeric particles.
CA002457247A CA2457247A1 (en) 2001-10-12 2002-10-04 A method of producing coloured plastics or coloured polymeric particles
DE60229153T DE60229153D1 (en) 2001-10-12 2002-10-04 PROCESS FOR PRODUCING COLORED PLASTICS OR POLYMERIC COLOR PARTICLES
US11/702,730 US20070130704A1 (en) 2001-10-12 2007-02-06 Method of producing mass colored beer bottles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH18842001 2001-10-12
CH20011884/01 2001-10-12

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/702,730 Continuation US20070130704A1 (en) 2001-10-12 2007-02-06 Method of producing mass colored beer bottles

Publications (2)

Publication Number Publication Date
WO2003033584A2 true WO2003033584A2 (en) 2003-04-24
WO2003033584A3 WO2003033584A3 (en) 2003-12-04

Family

ID=4566638

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/011167 WO2003033584A2 (en) 2001-10-12 2002-10-04 A method of producing coloured plastics or coloured polymeric particles

Country Status (11)

Country Link
US (2) US7193001B2 (en)
EP (1) EP1434818B1 (en)
JP (1) JP4312601B2 (en)
KR (1) KR20050033529A (en)
CN (1) CN1568345A (en)
AT (1) ATE409723T1 (en)
BR (1) BR0213174A (en)
CA (1) CA2457247A1 (en)
DE (1) DE60229153D1 (en)
MX (1) MXPA04002043A (en)
WO (1) WO2003033584A2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1434818B1 (en) * 2001-10-12 2008-10-01 Ciba Holding Inc. A method of producing coloured plastics or coloured polymeric particles
KR20140083615A (en) 2012-12-26 2014-07-04 제일모직주식회사 Photosensitive resin composition for color filter and color filter using the same
CN103788597B (en) * 2014-01-27 2016-01-20 泉州市约克颜料有限公司 UV color barrier agent and the manufacture craft containing UV color barrier agent PET bottle

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5131916A (en) * 1990-03-01 1992-07-21 Bayer Aktiengesellschaft Colored fluorescent polymer emulsions for marker pens: graft copolymers and fluorescent dyes in aqueous phase
US5550192A (en) * 1992-12-07 1996-08-27 Lyondell Petrochemical Company Dyeable polyolefin compositions and dyeing polyolefin compositions
EP0803772A2 (en) * 1996-04-23 1997-10-29 Agfa-Gevaert N.V. An imaging element and a method for producing a lithographic plate therewith
EP0829376A1 (en) * 1996-09-13 1998-03-18 Dai Nippon Printing Co., Ltd. Black thermal transfer sheet

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927063A (en) * 1966-09-09 1975-12-16 Ciba Geigy Ag Water-insoluble styryl dyestuffs
US4006178A (en) * 1971-09-24 1977-02-01 Ciba-Geigy Corporation Process for the manufacture of dicyanovinyl compounds
DD111920A5 (en) * 1973-04-04 1975-03-12
US4322487A (en) * 1979-08-08 1982-03-30 Eastman Kodak Company Composite electrically photosensitive particles for electrophoretic migration imaging process
US4359322A (en) * 1980-06-06 1982-11-16 Neal Chemical Company, Inc. Dyeing process
US5085903A (en) * 1990-06-11 1992-02-04 Ppg Industries, Inc. Coatings for the protection of products in light-transmitting containers
US5157067A (en) * 1990-06-27 1992-10-20 Ferro Corporation Liquid colorant/additive concentrate for incorporation into plastics
JPH06200200A (en) * 1993-01-06 1994-07-19 Seiko Epson Corp Ink composition for ink jet recording
US5324348A (en) * 1993-07-13 1994-06-28 Perret Jr Gerard A Disposable orthodontic wire marker
US6262153B1 (en) * 1998-10-12 2001-07-17 Clariant Finance (Bvi) Limited Colored wax articles
US6355723B1 (en) * 2000-06-22 2002-03-12 General Electric Co. Dark colored thermoplastic compositions, articles molded therefrom, and article preparation methods
US6423764B1 (en) * 2000-08-24 2002-07-23 Milliken & Company Method of producing colored polyester thermoplastic materials through specific solid-state procedures
US6716898B2 (en) * 2001-05-18 2004-04-06 Eastman Chemical Company Amber polyester compositions for packaging food and beverages
EP1434818B1 (en) * 2001-10-12 2008-10-01 Ciba Holding Inc. A method of producing coloured plastics or coloured polymeric particles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5131916A (en) * 1990-03-01 1992-07-21 Bayer Aktiengesellschaft Colored fluorescent polymer emulsions for marker pens: graft copolymers and fluorescent dyes in aqueous phase
US5550192A (en) * 1992-12-07 1996-08-27 Lyondell Petrochemical Company Dyeable polyolefin compositions and dyeing polyolefin compositions
EP0803772A2 (en) * 1996-04-23 1997-10-29 Agfa-Gevaert N.V. An imaging element and a method for producing a lithographic plate therewith
EP0829376A1 (en) * 1996-09-13 1998-03-18 Dai Nippon Printing Co., Ltd. Black thermal transfer sheet

Also Published As

Publication number Publication date
EP1434818A2 (en) 2004-07-07
BR0213174A (en) 2004-09-14
US7193001B2 (en) 2007-03-20
CA2457247A1 (en) 2003-04-24
WO2003033584A3 (en) 2003-12-04
EP1434818B1 (en) 2008-10-01
KR20050033529A (en) 2005-04-12
US20070130704A1 (en) 2007-06-14
JP4312601B2 (en) 2009-08-12
US20040254271A1 (en) 2004-12-16
ATE409723T1 (en) 2008-10-15
CN1568345A (en) 2005-01-19
JP2005505671A (en) 2005-02-24
DE60229153D1 (en) 2008-11-13
MXPA04002043A (en) 2004-06-07

Similar Documents

Publication Publication Date Title
EP1368431B1 (en) Pyridone dyes, a process for their preparation and their use in the production of coloured plastics or polymeric colour particles
US20070130704A1 (en) Method of producing mass colored beer bottles
EP1532196B1 (en) Method of producing coloured plastics or polymeric colour particles
EP1385912B1 (en) Pyridone dyes, a process for their preparation and their use in the production of coloured plastics or polymeric colour particles
EP2038339A2 (en) Method of protecting organic material from light
EP1697227A1 (en) Method of protecting organic material from light
MXPA06007267A (en) Method of protecting organic material from light

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REEP Request for entry into the european phase

Ref document number: 2002779464

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2002779464

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2457247

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2004/002043

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 10492182

Country of ref document: US

Ref document number: 20028200241

Country of ref document: CN

Ref document number: 1020047005299

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2003536320

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1012/CHENP/2004

Country of ref document: IN

WWP Wipo information: published in national office

Ref document number: 2002779464

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 2002779464

Country of ref document: EP