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WO2002066563A1 - Nouveaux monomeres colorants et nouvelles compositions copolymeres - Google Patents

Nouveaux monomeres colorants et nouvelles compositions copolymeres Download PDF

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Publication number
WO2002066563A1
WO2002066563A1 PCT/IB2002/000514 IB0200514W WO02066563A1 WO 2002066563 A1 WO2002066563 A1 WO 2002066563A1 IB 0200514 W IB0200514 W IB 0200514W WO 02066563 A1 WO02066563 A1 WO 02066563A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
aryl
dye
halogen
substituted
Prior art date
Application number
PCT/IB2002/000514
Other languages
English (en)
Inventor
Bansi Lal Kaul
Jean-Christophe Graciet
Original Assignee
Clariant International Ltd
Clariant Finance (Bvi) Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd, Clariant Finance (Bvi) Limited filed Critical Clariant International Ltd
Publication of WO2002066563A1 publication Critical patent/WO2002066563A1/fr

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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
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes

Definitions

  • This invention relates to copolymer compositions having pigment like properties, comprising a fluorescent or non-fluorescent dye attached to a polymer chain by a spacer.
  • the invention also relates to the respective new dye monomers.
  • Colorants not covalently bond in a polymer matrix tend to agglomerate and to crys ' talize leading to inhomogenous distribution of colorants within the matrix.
  • Fluorescent colorants in particular often loose their fluorescent properties by agglomeration of fluorescent sites (quenching). Furthermore with non covalently bond colorants, fading or bleading of the colorant occurs.
  • US 6,103,006 discloses fluorescent polymeric pigments with increased lightfastness obtained by the polycondensation of dye monomers with at least two functional groups like diamine, dialcohol or dicarboxylic acid.
  • the functional groups for the polycondensation are directly located at the dye moiety as in the anhydride or diacid form of the BXD A fluorescent dye.
  • the physical properties of polymers depend highly on the structure of the polymerisable moiety and the process of polymerization. Besides the above mentioned polycondensation process the polyreaction of chain growth polymers can be utilized to react dye monomers into a polymer backbone.
  • WO 99/21937 (3M) discloses a two phase interpenetrating polymer network system with a dye functionalized polymer in the second phase.
  • the optionally fluorescent dye is covalently bond to the polymer to slow migration and to enhance compatibility, e.g. a hydroxy functional dye (YGOH) is reacted into a polyurethane or an acrylate functional dye (YGOAcr) is reacted into a respective chain growth polymer.
  • YGOH hydroxy functional dye
  • YGOAcr an acrylate functional dye
  • the preferred fluorescent dye moieties are thioxanthene and perylene imide, at a content of 0,01 to 2 percent by weight (based on the total composition).
  • a problem of copolymerisation in general is, that each monomer has its own copolymerization parameters, in the extreme not being copolymerizable at all.
  • One objective of the invention is to allow variation of the dye moieties without significantly changing the copolymerization parameters of the dye monomers by separating the polymerizable moiety and the dye moiety from each other with a spacer. Further, the spacer is adjusted in chain length to enhance the dye properties in the matrix, especially the temperature stability and fluorescent properties, without significantly changing the physical polymer properties.
  • Another objective of the present invention is to provide a copolymer composition polymerizing to fine, uniform, regular particles in suspension polymerisation.
  • a further objective of the present invention is to provide a new copolymer composition with pigment like properties being easily applicable in the coloration of standard polymers.
  • the dye monomer is of the general formula (I)
  • Ri is C M 2 alkylene, C 1 -12 alkyoxylene, C ⁇ -io arylene, (C 6 _ ⁇ o) aryl-(C[. 6 ) alkylene or (C ⁇ . 6 ) alkyl-(C 6 . ⁇ 0 ) arylene, the alkylene and/or arylene radicals optionally being substituted by hydroxyl, C ⁇ - 6 alkoxyl, C 6 . ⁇ 0 aryloxy or halogen, X is oxygen or NR' with R' being C ⁇ . 6 alkyl, C 6 - ⁇ o aryl, (C 6 - ⁇ o) aryl-(C ⁇ - 6 ) alkyl or (C).
  • R is a polymerizable group
  • A is a substituted or unsubstituted aromatic or heterocyclic ring system of the general formula (Ila) to (Na)
  • R" is hydrogen, C e alkyl, C ⁇ -io aryl, (C 6 - ⁇ o) aryl-(C ⁇ - 6 ) alkyl or (C ⁇ _ 6 ) alkyl-(C 6 . 10) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, . 6 alkoxyl, C ⁇ -io aryloxy or halogen, R 3 is hydrogen, halogen, ⁇ R 4 R 5 , R 5 O or R 5 S, in which R 4 is hydrogen C ⁇ .
  • R 5 is C ⁇ - 6 alkyl, C 6 . 10 aryl, (C 6 . ⁇ 0 ) aryl-(C ⁇ _ 6 ) alkyl or (C ⁇ - 6 ) alkyl-(C 6 . ⁇ 0 ) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, C ⁇ . 6 alkoxyl, C ⁇ -io aryloxy or halogen.
  • the ring labeled B is fused on in 1 ,2-, 2,3- or 3,4- position and is selected from the group consisting of the moieties (1) to (8)
  • R 7 and R 8 are, independently from each other, hydrogen, C ⁇ _ 8 alkyl, C 5 . 6 cycloalkyl, benzyl, benzanilide, phenyl or naphthyl whereby benzanilide, phenyl and naphthyl groups may be mono- or poly-substituted by radicals selected from the group halogen, nitro, C ⁇ . 8 alkyl, C 5 . 6 cycloalkyl, benzyl, phenyl or naphthyl, COOalkyl, C ⁇ _ 3 alkoxy or trifluoromethyl and R is, independently from R and R 8 , hydrogen, hydroxy, C ⁇ . 8 alkyl, C 5 .
  • the Ring B is annelated in 3,4-position with a group of the formula - NR 7 (CO) ⁇ -NR 8 - or -O-CO-NR 7 - , n is 1 or 2, R 7 and R 8 are independently hydrogen, Q. 6 alkyl, C ⁇ -io aryl, (C 6 - ⁇ o) aryl-(C ⁇ - 6 )alkyl or (C ⁇ - 6 )alkyl-(C 6 - ⁇ o)aryl, the alkyl and or aryl radicals optionally being substituted by amino, C ⁇ . 6 alkylamino, C 6 _ ⁇ 0 cycloalkylamino, hydroxyl, C ⁇ _ 6 alkoxyl, C 6 - ⁇ o aryloxy or halogen.
  • the preferred spacer Ri is a . ⁇ 2 alkylene, more preferred C 3 . 8 alkylene, most preferably C 6 alkylene.
  • Preferred polymerizable groups for R are methylmethacrylate, methacrylate or acrylate, most preferably methylmethacrylate.
  • Preferred co-monomers for the copolymer composition are methacrylate, methylmethacrylate, styrene and vinyl type monomers.
  • the preferred content of the polymerizable monomer in a copolymer composition according to the invention is from 0.01 to 10, more preferably from 1 to 5 and most preferably between 2 and 3 percent by weight based on the total weight of the copolymer composition.
  • the dye monomers of formulae (I) are obtained by the reaction of the dye moiety functionalized with a leaving group (L), e.g. chlorine or bromine, with an amino alcohol or diamine comprising the respective spacer.
  • L e.g. chlorine or bromine
  • the hydroxy or amino group on the free end of the spacer can be further functionalized under acid or basic conditions with acrylic or methacrylic acid or derivates thereof, such as the acid chloride.
  • the final product is obtained in high yield.
  • A, Ri and X are defined as above, L is a leaving group and G is hydrogen or methyl.
  • Preferred dye monomers according to the invention are those of the general formulae (IV) and (V),
  • the copolymerization of the dye monomers according to the invention is usually carried out as a radical initiated suspension (or miniemulsion) polymerisation in water together with the respective chain growth monomer, such as acrylate, methacrylate or styrene.
  • the copolymer is obtained as fine latex particles of very uniform and regular shape.
  • the range of particle size obtained by this copolymerization process is 10 to 500 nm, preferably 20 to 200 nm and most preferably from 40 to 150 nm.
  • the copolymer pigments according to the invention are suitable for the mass pigmentation of substrates including synthetic polymers, synthetic resins and regenerated fibers optionally in the presence of solvents.
  • substrates more particularly include oil, water and solvent based surface coatings, polyester spinning melts, polyethylene, polystyrene and polyvinyl chloride melts, polymethacrylate and polymethylmethacrylate melts, polyuethane masses,, rubber and synthetic leather.
  • the pigments can be used in the manufacture of printing inks, for the mass coloration of paper and for coating and printing textiles.
  • copolymer pigments according to the invention are also suitable as colorants in electrophotographic toners and developers, such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and specialty toners.
  • electrophotographic toners and developers such as one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and specialty toners.
  • Typical toner binders are addition polymerization, polyaddition and polycondensation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, polysulphones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may comprise further constituents, such as charge control agents, waxes or flow assistants, or may be modified subsequently with these additives.
  • polyaddition and polycondensation resins such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, polysulphones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may comprise further constituents, such as charge control agents, waxes or flow assistants, or may be modified subsequently with these additives.
  • copolymer pigments according to the invention are suitable, furthermore, as colorants in powders and powder coating materials, especially in triboelectrically or electrokinetically sprayable powder coating materials which are used for the surface coating of articles made, for example, from metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber.
  • Powder coating resins that are typically employed are epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethane resins and acrylic resins, together with customary hardeners. Combinations of resins are also used. For example, epoxy resins are frequently employed in combination with carboxyl- and hydroxyl-containing polyester resins.
  • Typical hardener components are, for example, acid anhydrides, imidazoles and also dicyanodiamide and its derivatives, blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
  • copolymer pigments according to the invention are suitable as colorants in ink-jet inks, both aqueous and non-aqueous, and in those inks, which operate in accordance with the hot-melt process.
  • Example 1 4-bromonaphthalic anhydride (10 part) is suspended in N-methylpyrrolidone (30 parts) in presence of 1 part of -toluenesulfonic acid. 4 parts of ⁇ -diaminobenzene are added and the reaction mixture is stirred to 150°C. When the reaction is completed, the mixture is cooled to 25°C, filtered and washed with methanol. After drying under vacuum, 1 1 parts of a pale yellow powder are obtained (85% yield). This product is then suspended in 28 parts of methylamino-propylamine and the resulting suspension is heated to 130°C until reaction is completed. The mixture is cooled to 95°C and poured into water at 90°C. After stirring and cooloing to 25°C , the orange suspension is filterd and washed with water until no amine remains in the presscake. After drying, 10.7 parts of an orange-red powder are obtained (95% yield).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des compositions copolymères présentant les caractéristiques des pigments, comprenant un colorant fluorescent ou non-fluorescent relié à une chaîne polymérique par un espaceur. La présente invention concerne également des nouveaux monomères colorants mono et difonctionnels comprenant un groupe polymérisable relié à un fragment de colorant par un espaceur. Les pigments polymères présentent d'excellentes propriétés, en particulier, une stabilité à haute température et une applicabilité facile en tant que colorant dans différents polymères types. .
PCT/IB2002/000514 2001-02-21 2002-02-20 Nouveaux monomeres colorants et nouvelles compositions copolymeres WO2002066563A1 (fr)

Applications Claiming Priority (2)

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GB0104238.1 2001-02-21
GB0104238A GB0104238D0 (en) 2001-02-21 2001-02-21 New dye monomers and copolymer compositions having pigment like properties

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WO2002066563A1 true WO2002066563A1 (fr) 2002-08-29

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2867779A1 (fr) * 2004-03-19 2005-09-23 Oreal Composes monomeriques possedant des proprietes optiques, polymeres les comprenant et utilisation
EP1580205A1 (fr) * 2004-03-26 2005-09-28 L'oreal Nouveaux polymères séquencés, compositions les comprenant, procédés et utilisation
WO2005100359A1 (fr) * 2004-03-19 2005-10-27 L'oreal Composition comprenant un compose monomerique a effet optique, procede employant ladite composition, compose monomerique et polymere le comprenant
FR2871161A1 (fr) * 2004-06-08 2005-12-09 Oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
FR2871160A1 (fr) * 2004-06-08 2005-12-09 Oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
WO2006005822A1 (fr) * 2004-06-08 2006-01-19 L'oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
WO2006005823A1 (fr) * 2004-06-08 2006-01-19 L'oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
US7662461B2 (en) 2006-03-31 2010-02-16 Milliken & Company Synthetic leather articles and methods for producing the same
US7872069B2 (en) 2006-03-31 2011-01-18 Milliken & Company Coated substrates and polymer dispersions suitable for use in making the same
WO2012160521A1 (fr) 2011-05-24 2012-11-29 Ecole Polytechnique Federale De Lausanne (Epfl) Films de conversion de couleur comprenant des colorants fluorescents organiques substitués par un polymère
US8431648B2 (en) 2006-03-31 2013-04-30 Milliken & Company Coated substrates and polymer dispersions suitable for use in making the same
WO2021206059A1 (fr) * 2020-04-07 2021-10-14 オリヱント化学工業株式会社 Colorant, mélange maître le contenant, composition de résine colorée et article moulé

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728745A1 (fr) * 1995-02-21 1996-08-28 Bayer Ag Dérivés de la 1,8-naphtalimides, procédé pour leur préparation et leur utilisation comme intermédiaires

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728745A1 (fr) * 1995-02-21 1996-08-28 Bayer Ag Dérivés de la 1,8-naphtalimides, procédé pour leur préparation et leur utilisation comme intermédiaires

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YAN, XIAO-LI ET AL: "Fluorescence property of two naphthalimide derivatives and their polymers", XP002203163, retrieved from STN Database accession no. 133:135636 *
GANGUANG KEXUE YU GUANG HUAXUE (2000), 18(2), 112-120 *
XUHONG Q ET AL: "THE SYNTHESIS, APPLICATION AND PREDICTION OF STOKES SHIFT IN FLUORESCENT DYES DERIVED FROM 1,8-NAPHTHALIC ANHYDRIDE", DYES AND PIGMENTS, ELSEVIER APPLIED SCIENCE PUBLISHERS. BARKING, GB, vol. 11, no. 1, 1989, pages 13 - 20, XP000026521, ISSN: 0143-7208 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2867779A1 (fr) * 2004-03-19 2005-09-23 Oreal Composes monomeriques possedant des proprietes optiques, polymeres les comprenant et utilisation
WO2005100359A1 (fr) * 2004-03-19 2005-10-27 L'oreal Composition comprenant un compose monomerique a effet optique, procede employant ladite composition, compose monomerique et polymere le comprenant
EP1580205A1 (fr) * 2004-03-26 2005-09-28 L'oreal Nouveaux polymères séquencés, compositions les comprenant, procédés et utilisation
FR2868074A1 (fr) * 2004-03-26 2005-09-30 Oreal Nouveaux polymeres, compositions les comprenant, procedes et utilisation
FR2871161A1 (fr) * 2004-06-08 2005-12-09 Oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
FR2871160A1 (fr) * 2004-06-08 2005-12-09 Oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
WO2006005822A1 (fr) * 2004-06-08 2006-01-19 L'oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
WO2006005823A1 (fr) * 2004-06-08 2006-01-19 L'oreal Dispersion de particules de polymere ethylenique, composition la comprenant et procede de traitement
US7662461B2 (en) 2006-03-31 2010-02-16 Milliken & Company Synthetic leather articles and methods for producing the same
US7824737B2 (en) 2006-03-31 2010-11-02 Milliken & Company Synthetic leather articles and methods for producing the same
US7872069B2 (en) 2006-03-31 2011-01-18 Milliken & Company Coated substrates and polymer dispersions suitable for use in making the same
US8431648B2 (en) 2006-03-31 2013-04-30 Milliken & Company Coated substrates and polymer dispersions suitable for use in making the same
WO2012160521A1 (fr) 2011-05-24 2012-11-29 Ecole Polytechnique Federale De Lausanne (Epfl) Films de conversion de couleur comprenant des colorants fluorescents organiques substitués par un polymère
WO2021206059A1 (fr) * 2020-04-07 2021-10-14 オリヱント化学工業株式会社 Colorant, mélange maître le contenant, composition de résine colorée et article moulé
CN115443313A (zh) * 2020-04-07 2022-12-06 东方化学工业株式会社 一种着色剂和包含其的母料、着色树脂组合物以及成型物
EP4134396A4 (fr) * 2020-04-07 2025-01-29 Orient chemical ind co ltd Colorant, mélange maître le contenant, composition de résine colorée et article moulé

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