WO2002066563A1 - New dye monomers and copolymer compositions - Google Patents
New dye monomers and copolymer compositions Download PDFInfo
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- 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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- 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).
Abstract
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 provides for new mono- and difunctional dye monomers comprising a polymerizable group attached to a dye moiety by a spacer.The polymer pigments provide excellent properties, especially high temperature stability and easy applicability as colorant in different standard polymers.
Description
NEW DYE MONOMERS AND COPOLYMER COMPOSITIONS
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.
Articles containing colorants are known to loose their color when exposed to solar radiation for extended times. In particular, fluorescent colorants degrade more quickly than conventional colorants, often turning colorless on exposure to daily solar radiation within days or months.
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 (DiPietro) 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.
YGOAcr (WO 99/21937)
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.
These objectives are achieved by a copolymer composition comprising a new dye monomer, in which the dye moiety of the monomer is separated from the polymerizable moiety by a spacer.
The dye monomer is of the general formula (I)
A-N— R— XR (I) H 1
in which Ri is CM 2 alkylene, C1-12 alkyoxylene, Cβ-io arylene, (C6_ιo) aryl-(C[.6) alkylene or (Cι.6) alkyl-(C6.ι0) arylene, the alkylene and/or arylene radicals optionally being substituted by hydroxyl, Cι-6 alkoxyl, C6.ι0 aryloxy or halogen, X is oxygen or NR' with R' being Cι.6 alkyl, C6-ιo aryl, (C6-ιo) aryl-(Cι-6) alkyl or (C).6) alkyl-(C6.ιo) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, Cι-6 alkoxyl, C6.ιo aryloxy or halogen, R is a polymerizable group, and
A is a substituted or unsubstituted aromatic or heterocyclic ring system of the general formula (Ila) to (Na)
(lla) (Ilia) (IVa) (Va)
wherein R" is hydrogen, C e alkyl, Cβ-io aryl, (C6-ιo) aryl-(Cι-6) alkyl or (Cι_6) alkyl-(C6. 10) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, .6 alkoxyl, Cβ-io aryloxy or halogen, R3 is hydrogen, halogen, ΝR4R5, R5O or R5S, in which
R4 is hydrogen Cι.6 alkyl, C6.ιo aryl, (C6-ιo) aryl-(Cι-6) alkyl or (Cι-6) alkyl-(C6.ιo) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, Cι_6 alkoxyl, C6. ιo aryloxy or halogen;
R5 is Cι-6 alkyl, C6.10 aryl, (C6.ι0) aryl-(Cι_6) alkyl or (Cι-6) alkyl-(C6.ι0) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, Cι.6 alkoxyl, Cβ-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)
wherein R7 and R8 are, independently from each other, hydrogen, Cι_8alkyl, C5.6 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, Cι.8alkyl, C5.6cycloalkyl, benzyl, phenyl or naphthyl, COOalkyl, Cι_3 alkoxy or trifluoromethyl and R is, independently from R and R8, hydrogen, hydroxy, Cι.8alkyl, C5.6 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, Cι.8alkyl, C5.6cycloalkyl, benzyl, phenyl or naphthyl, COOalkyl, Cι.3alkoxy or trifluoromethyl.
Preferred, the Ring B is annelated in 3,4-position with a group of the formula - NR7(CO)π-NR8- or -O-CO-NR7- , n is 1 or 2, R7 and R8 are independently hydrogen, Q. 6 alkyl, Cβ-io aryl, (C6-ιo) aryl-(Cι-6)alkyl or (Cι-6)alkyl-(C6-ιo)aryl, the alkyl and or aryl radicals optionally being substituted by amino, Cι.6 alkylamino, C6_ι0 cycloalkylamino, hydroxyl, Cι_6 alkoxyl, C6-ιo aryloxy or halogen.
The preferred spacer Ri is a .ι2 alkylene, more preferred C3.8 alkylene, most preferably C6 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.
A-L H2N- -Rr- XH *- A-N — R.—XH
-HL H 1
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.
Preferred dye monomers according to the invention are those of the general formulae (IV) and (V),
(IV)
(V) wherein R, Ri and X are defined as above and R3 is hydrogen.
Other preferred dye monomers according to the invention are those of the general formula (III)
(III) wherein R, Ri and X are defined as above and the Ring B is annelated in 3,4-position with a group of the formula -NR7(CO)n-NR8-, n is 1 or 2, R7 and R8 are independently hydrogen or Cι.6 alkyl.
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. These 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. Furthermore, the pigments can be used in the manufacture of printing inks, for the mass coloration of paper and for coating and printing textiles.
The 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.
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.
The 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 (as a function of the resin system) 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.
In addition, the 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.
The following examples illustrate the invention. Unless otherwise specified, parts and percentages used in the examples are on a weight to weight basis.
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 ø-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).
Example 2
4-bromonaphthalic anhydride (10 parts) is suspended in N-methylpyrrolidone (40 parts) in presence of 1 part of p-toluenesulfonic acid. 6 parts of 1,4- diaminobenzimidazolone are added and the reaction mixture is stirred to 150°C under
nitrogen atmosphere. When the reaction is completed, the mixture is cooled to 25°C, filtered and washed with methanol. After drying under vacuum, 10 parts of an orange- red powder are obtained (67% yield). This product is then suspended in 40 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 cooling to 25°C , the red-orange suspension is filtered and washed with water until no amine remains in presscake. After drying, 8.6 parts of an orange-red powder are obtained (85% yield).
Example 3
4-bromonaphthalic anhydride (10 parts) is suspended in N-methylpyrrolidone (40 parts) in presence of 1 part of/7-toluenesulfonic acid. 6 parts of 1,8-diaminonaphthalene are added and the reaction mixture is stirred to 150°C under nitrogen atmosphere. When the reaction is completed, the mixture is cooled to 25°C, filtered and washed with methanol. After drying under vacuum, 13.2 parts of a violet powder are obtained (94% yield). This product is then suspended in 40 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 cooling to 25°C , the violet suspension is filterd and washed with water until no amine remains in presscake. After drying, 9.2 parts of a violet powder are obtained (71% yield).
20 parts of the methylaminopropyl functionalized dye are suspended into 75 parts of o- dichlorobenzene in presence of 5.7 parts of triethylamine. The mixture is then heated to 130° C and methacryloyl chloride (5.9 parts) is added over 45 minutes at this temperature. After reaction completion, the resulting yellow solution is cooled to room temperature and filtered. The presscake is washed with methanol and dried. 21 parts of bright yellow powder are obtained (90% yield);
Claims
A dye monomer, characterized in that the dye moiety is of the formula (I)
A-N— Rr-XR (1)
H 1
with Ri is Ci-12 alkylene, CM2 alkyoxylene, C6-ιo arylene, (C6.ιo) aryl-(Cu6) alkylene or (Cι-6) alkyl-(,C6-ιo) arylene, the alkylene and/or arylene radicals optionally being substituted by hydroxyl, Cι-6 alkoxyl, C6.ιo aryloxy or halogen,
X is oxygen or NR' with R' being Cι.6 alkyl, C6_ι0 aryl, (C6_ιo) aryl-(Cι_6) alkyl or (Cι-6) alkyl-(C6-ι0) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, C].6 alkoxyl, C6-ιo aryloxy or halogen,
R is a polymerizable group,
A is a substituted or unsubstituted aromatic or heterocyclic ring system of the general formulae (Ila), (Ilia), (IVa) or (Va)
(Ila) (Ilia) (IVa) (Va)
wherein R" is hydrogen, Cι.6 alkyl, Cδ-io aryl, (C6.10) aryl-(Cι-6) alkyl or (Cue) alkyl-(C6.ιo) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, Cι_6 alkoxyl, C6_ι0 aryloxy or halogen, the Ring B is annelated in 3,4-position with a group of the formula -NR7(CO)n- NR8- or -O-CO-NR - , n is 1 or 2, R7 and R8 are independently hydrogen, C(.6 alkyl, C6.ι0 aryl, (C6-ιo) aryl-(Cι.6)alkyl or (Cι.6)alkyl-(C6.ι0)aryl, the alkyl and/or aryl radicals optionally being substituted by amino, C[.6 alkylamino, C6.ι0 cycloalkylamino, hydroxyl, Cι_6 alkoxyl, C6-ιo aryloxy or halogen,
R is hydrogen, halogen, NR4R5, R5O or R5S, in which
R4 is hydrogen Cι.6 alkyl, C6.ι0 aryl, (C6-ιo) aryl-(Cι-6) alkyl or (Cι_6) alkyl-(C6. ιo) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, C]-6 alkoxyl, C6.ιo aryloxy or halogen; R5 is Cue alkyl, C6-ιo aryl, (C6.ιo) aryl-(Cι.6) alkyl or (Cι.6) alkyl-(C6.ιo) aryl, the alkyl and/or aryl radicals optionally being substituted by hydroxyl, Cι-6 alkoxyl, C6-ιo aryloxy or halogen.
2. A dye monomer according to claim 1 characterized in that R) has a chain lenght of C to C8, preferably of C6.
3. A dye monomer according to claim 1 or 2 characterized in that the polymerizable moiety R is a methacrylate or methylmethacrylate group.
4. A process for the preparation of a dye monomer according to claims 1 to 3 characterised in that a hydroxy or amino functionalized dye moiety is reacted to a polymerizable moiety.
4. A copolymer composition comprising a dye monomer according to claims I to 3.
5. A copolymer composition according to claim 4 characterised in that it comprises as a comonomer a monomer of the methacrylate, methylmethacrylate, styrene or vinyl type.
6. A copolymer composition according to claims 4 or 5 characterized in that the preferred content of the dye monomer in the copolymer composition is between 0.01 and 10 percent by weight.
7. A process for the preparation of a copolymer composition according to claims 4 to 6 characterised in that at least a dye monomer according to claims 1 to 3 is mixed with at least a copolymerizable monomer before the polyreaction.
A process for the copolymerization of dye monomers according to claims 1 to 3, characterized in that the copolymerization is carried out as suspension polymerization.
9. Copolymer particles having pigment like properties obtained by copolymerization of a dye monomer of claim 1 to 3 with copolymerizable monomers.
10. Use of copolymer particles according to claim 9 as pigment.
11. A polymerproduct comprising as a pigment copolymer particles according to claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0104238A GB0104238D0 (en) | 2001-02-21 | 2001-02-21 | New dye monomers and copolymer compositions having pigment like properties |
| GB0104238.1 | 2001-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002066563A1 true WO2002066563A1 (en) | 2002-08-29 |
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ID=9909186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2002/000514 WO2002066563A1 (en) | 2001-02-21 | 2002-02-20 | New dye monomers and copolymer compositions |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB0104238D0 (en) |
| WO (1) | WO2002066563A1 (en) |
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| EP1580205A1 (en) * | 2004-03-26 | 2005-09-28 | L'oreal | New block polymers, compositions comprising the same and use thereof |
| WO2005100359A1 (en) * | 2004-03-19 | 2005-10-27 | L'oreal | Composition containing a monomer compound exhibiting an optical property, method making use of said composition, a monomer compound and polymer containing said compound |
| FR2871160A1 (en) * | 2004-06-08 | 2005-12-09 | Oreal | Particles dispersion in organic or non aqueous medium, useful as e.g. make-up product, comprises ethylinic polymer comprising skeleton insoluble in the medium and part soluble in the medium containing lateral chains in covalent manner |
| FR2871161A1 (en) * | 2004-06-08 | 2005-12-09 | Oreal | Dispersion (solid particles), useful as e.g. make-up product, comprises ethylinic polymer comprising a structure (insoluble and partly soluble in the medium) containing lateral chains in covalent manner |
| WO2006005822A1 (en) * | 2004-06-08 | 2006-01-19 | L'oreal | Dispersion of ethylene polymer particles, composition containing same and treatment method |
| WO2006005823A1 (en) * | 2004-06-08 | 2006-01-19 | L'oreal | Dispersion of ethylene polymer particles, composition containing same and treatment method |
| 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 (en) | 2011-05-24 | 2012-11-29 | Ecole Polytechnique Federale De Lausanne (Epfl) | Color conversion films comprising polymer-substituted organic fluorescent dyes |
| US8431648B2 (en) | 2006-03-31 | 2013-04-30 | Milliken & Company | Coated substrates and polymer dispersions suitable for use in making the same |
| WO2021206059A1 (en) * | 2020-04-07 | 2021-10-14 | オリヱント化学工業株式会社 | Colorant, master batch containing same, colored resin composition, and molded article |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728745A1 (en) * | 1995-02-21 | 1996-08-28 | Bayer Ag | 1,8-Naphthalimid derivates, process for their preparation and their use as intermediates |
-
2001
- 2001-02-21 GB GB0104238A patent/GB0104238D0/en not_active Ceased
-
2002
- 2002-02-20 WO PCT/IB2002/000514 patent/WO2002066563A1/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0728745A1 (en) * | 1995-02-21 | 1996-08-28 | Bayer Ag | 1,8-Naphthalimid derivates, process for their preparation and their use as intermediates |
Non-Patent Citations (3)
| 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 (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2867779A1 (en) * | 2004-03-19 | 2005-09-23 | Oreal | New naphthadiazabenzoanthracen-7-one derivatives, useful in a composition conferring the optical effects (particularly fluorescence) |
| WO2005100359A1 (en) * | 2004-03-19 | 2005-10-27 | L'oreal | Composition containing a monomer compound exhibiting an optical property, method making use of said composition, a monomer compound and polymer containing said compound |
| EP1580205A1 (en) * | 2004-03-26 | 2005-09-28 | L'oreal | New block polymers, compositions comprising the same and use thereof |
| FR2868074A1 (en) * | 2004-03-26 | 2005-09-30 | Oreal | NOVEL POLYMERS, COMPOSITIONS COMPRISING SAME, METHODS AND USE |
| WO2006005822A1 (en) * | 2004-06-08 | 2006-01-19 | L'oreal | Dispersion of ethylene polymer particles, composition containing same and treatment method |
| FR2871161A1 (en) * | 2004-06-08 | 2005-12-09 | Oreal | Dispersion (solid particles), useful as e.g. make-up product, comprises ethylinic polymer comprising a structure (insoluble and partly soluble in the medium) containing lateral chains in covalent manner |
| FR2871160A1 (en) * | 2004-06-08 | 2005-12-09 | Oreal | Particles dispersion in organic or non aqueous medium, useful as e.g. make-up product, comprises ethylinic polymer comprising skeleton insoluble in the medium and part soluble in the medium containing lateral chains in covalent manner |
| WO2006005823A1 (en) * | 2004-06-08 | 2006-01-19 | L'oreal | Dispersion of ethylene polymer particles, composition containing same and treatment method |
| 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 (en) | 2011-05-24 | 2012-11-29 | Ecole Polytechnique Federale De Lausanne (Epfl) | Color conversion films comprising polymer-substituted organic fluorescent dyes |
| WO2021206059A1 (en) * | 2020-04-07 | 2021-10-14 | オリヱント化学工業株式会社 | Colorant, master batch containing same, colored resin composition, and molded article |
| CN115443313A (en) * | 2020-04-07 | 2022-12-06 | 东方化学工业株式会社 | Coloring agent, master batch containing coloring agent, coloring resin composition and molded object |
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| Publication number | Publication date |
|---|---|
| GB0104238D0 (en) | 2001-04-11 |
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